Multi-staged catalyst systems and process for converting alkanes to alkenes and to their corresponding oxygenated products

ABSTRACT

Alkenes, unsaturated saturated carboxylic acids, saturated carboxylic acids and their higher analogues are prepared cumulatively from corresponding alkanes utilizing using a multi-staged catalyst system and a multi-stage process which comprises steam cracking of alkanes to corresponding alkenes at flame temperatures and at short contact times in combination with one or more oxidation catalysts for catalytically converting the corresponding alkenes to further corresponding oxygenated products using short contact time reactor conditions.

CROSS REFERENCE TO RELATED PATENT APPLICATIONS

This non-provisional application is a divisional of non-provisional U.S.patent application Ser. No. 11/269,434 filed Nov. 8, 2005, now allowed,benefit of which is claimed under 35 U.S.C. §120 and which in turnclaims benefit under 35 U.S.C. §119(e) of U.S. provisional ApplicationNo. 60/629,989 filed Nov. 22, 2004, priority benefit of which is alsoclaimed for the present divisional application.

The present invention relates to alkane oxidation/dehydrogenationcatalysts and processes for converting alkanes and oxygen todehydrogenated products and/or oxygenated products at flametemperatures. More particularly, the present invention is directed to amulti-staged process which includes but is not limited to convertingalkanes to corresponding alkenes by steam cracking followed byconverting alkenes to the corresponding oxygenated products under shortcontact time reactor conditions. In addition, the present invention isdirected to catalyst systems for converting specific alkanes to theircorresponding alkenes and oxygenates including unsaturated carboxylicacids, saturated carboxylic acids, esters of unsaturated carboxylicacids and their respective higher analogues in a short contact timereactor at flame temperatures; to a method for making the catalystsystems; and to a hybrid process for the gas phase catalytic oxidationof alkanes using the catalyst systems. The invention is also directed tocatalyst systems for converting saturated carboxylic acids to theircorresponding unsaturated carboxylic acids and to higher analogue estersof unsaturated carboxylic acids and to a multi-staged process for thegas phase catalytic oxidation of saturated carboxylic acids. Theinvention is also directed to a multi-staged process for the gas phaseoxidation of alkanes that includes the staging of additional feedsincluding alkenes, oxygen, formaldehyde and alcohols for preparingunsaturated carboxylic acids, esters of unsaturated carboxylic acids andtheir respective higher analogues using the catalyst systems.

The selective partial oxidation of alkenes to unsaturated carboxylicacids and their corresponding esters is an important commercial process.However, the selective partial oxidation/dehydrogenation of alkanes toproducts including olefins, unsaturated carboxylic acids and esters ofunsaturated carboxylic acids is an important industrial problem with anumber of challenges to overcome. One limitation of short contact timeoxidative dehydrogenation of alkanes concerns the first step, namely thelow yields associated with converting alkanes to their correspondingalkenes due to several competing reactions, including but not limited tofor example, over oxidation which leads to CO, CO₂, water, alkanefragments (Cn-m) and alkene fragments (C2n-m). The relatively lowselectivity of using mixed metal oxide catalysts to convert alkanes totheir corresponding alkenes under short contact time reactor conditionsis due to several factors including, but not limited to for example, thefollowing: (a) the catalyst generating flame temperature conditions alsotends to catalyze over oxidation reactions of the alkanes andcorresponding alkenes; (b) relatively low alkanes/oxygen ratios, neededto sustain the flame temperature conditions, which also tends tocatalyze over oxidation reactions of the alkanes and correspondingalkenes; (c) the overall reaction kinetics favor oxidation of alkanes toCO and carbon dioxide over desired oxidative dehydrogenation products,including corresponding alkenes.

U.S. Pat. No. 5,705,684 describes a process for preparing acrolein andacrylic acid from propane using different multi-metal oxide catalysts instages. In a first stage, propane is dehydrogenated with a Mo—Bi—Feoxide catalyst to propylene, which is used in a second stage as a feedto an oxidation reactor containing a Mo—V oxide catalyst and contactedwith oxygen to produce a mixture of acrolein and acrylic acid. However,the endothermic process requires a costly removal of hydrogen in thefirst stage, rendering the process prohibitive on a commercial scale. Inaddition, at flame temperatures the Mo—Bi—Fe oxide catalyst described isthermally unstable. Inventors have discovered a unique, efficient andcommercially feasible multi-staged solution for converting specificalkanes to their corresponding alkenes and oxygenated products includingunsaturated carboxylic acids, saturated carboxylic acids and esters ofunsaturated carboxylic acids using novel catalyst systems at flametemperatures in a short contact time reactor combined with a steamcracking of corresponding alkanes as the initial step. In addition,catalysts for converting saturated carboxylic acids to theircorresponding unsaturated carboxylic acids and to higher analogue estersof unsaturated carboxylic acids at flame temperatures in a short contacttime reactor and using the multi-staged method have been discovered. Toimprove the overall yields and selectivities of catalytically convertingalkanes to corresponding alkenes, inventors have discovered amulti-staged process that includes steam cracking of alkanes followed byreacting correspondingly produced alkenes to further correspondingoxygenated products under short contact time reactor conditions. Inanother multi-staged process, for example, small amounts ofcorresponding alkanes are reacted with stoichiometric amounts of oxygensufficient for total oxidation to carbon dioxide and water. The hotgaseous stream of carbon dioxide and steam is directed into a crackingzone, including a conventional cracking catalyst known in the art. Theheated steam has duel purposes to heat the cracking catalyst bed and toprovide steam for the cracking process. The remaining major amounts ofcorresponding alkanes will be combined with the carbon dioxide steammixture under turbulent flow conditions. The mixture of gases are thendirected to contact the cracking catalyst to provide correspondingalkenes in higher yields and selectivities. The converted correspondingalkenes are then further catalytically converted to correspondingoxygenates under short contact time reactor conditions. In anothermulti-staged process, for example, alkenes produced from dehydrogenationof alkanes using such catalysts are deliberately produced as in-processchemical intermediates by steam cracking and not isolated beforeselective partial oxidation to oxygenated products.

Several advantages of the present invention include but are not limitedto for example a lowered capital investment based upon reduced reactorsize, energy savings due to the sacrificial alkane burning for light offand heat generation, eliminates the need for an additional steamintegration step since the multi-staged method generates its own steamin the first phase (cracking step), readily achieves the thermodynamiclimits of alkene production with minimal catalyst investment andmaintenance.

Accordingly, the present invention provides a multi-stage catalystsystem comprising: at least one cracking catalyst for converting alkanesto their corresponding alkenes at flame temperatures and at shortcontact times and at least one oxidation catalyst for further convertingcorresponding alkenes to their corresponding oxygenated productsincluding, but not limited to for example, saturated carboxylic acidsand unsaturated carboxylic acids at flame temperatures and at shortcontact times, the at least one oxidation catalyst comprising: (a) atleast one metal selected from the group consisting of Ag, Au, Ir, Ni,Pd, Pt, Rh, Ru, alloys thereof and combinations thereof; and (b) atleast one modifier selected from the group of metal oxides including themetals Bi, In, Mg, P, Sb, Zr, Group 1-3 metals, lanthanide metals andcombinations thereof, in combination with or without (c) at least onemetal oxide including the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Nb, Ta, V,Zn, binary combinations thereof, ternary combinations thereof and highercombinations thereof; wherein the catalysts are impregnated on a metaloxide support.

According to a separate embodiment the multi-staged catalyst systemincludes an additional catalyst for converting saturated carboxylicacids to their corresponding unsaturated carboxylic acids at shortcontact times comprising: at least one metal oxide including the metalsMo, Fe, P, V and combinations thereof.

The invention provides a multi-staged catalyst bed for cumulativelyconverting alkanes to their corresponding alkenes saturated carboxylicacids and unsaturated carboxylic acids comprising: (a) a first catalystlayer comprising: at least one steam cracking catalyst at flametemperatures and at short contact times; (b) a second catalyst layerfurther comprising: (i) at least one metal selected from the groupconsisting of Ag, Au, Ir, Ni, Pd, Pt, Rh, Ru, alloys thereof andcombinations thereof; and (ii) at least one modifier selected from thegroup of metal oxides including the metals Bi, In, Mg, P, Sb, Zr, Group1-3 metals, lanthanide metals and combinations thereof, in combinationwith or without (iii) at least one metal oxide including the metals Cd,Co, Cr, Cu, Fe, Mn, Ni, Nb, Ta, V, Zn, binary combinations thereof,ternary combinations thereof and higher combinations thereof, whereinthe catalysts of the first layer are impregnated on a metal oxidesupport; and (c) a third catalyst layer comprising at least one metaloxide including the metals Mo, Fe, P, V and combinations thereof,wherein the catalyst of the third layer is impregnated on a metal oxidesupport and is oriented downstream from the second catalyst layer and isoriented further downstream from the first catalyst layer to increasethe overall yield of unsaturated carboxylic acid from its correspondingalkane.

According to a separate embodiment, the catalyst bed includes anadditional catalyst layer for converting saturated carboxylic acids totheir corresponding higher analogue unsaturated carboxylic acids andesters of unsaturated carboxylic acids at short contact timescomprising: at least one metal oxide including the metals V, Nb, Ta andcombinations thereof. The invention provides a multi-staged catalyst bedfor cumulatively converting alkenes to their corresponding unsaturatedcarboxylic acids, esters of unsaturated carboxylic acids and theirrespective higher analogues comprising comprising:

-   -   (a) a first catalyst layer comprising: at least one steam        cracking catalyst at flame temperatures and at short contact        times;    -   (b) a second catalyst layer further comprising: (i) at least one        metal selected from the group consisting of Ag, Au, Ir, Ni, Pd,        Pt, Rh, Ru, alloys thereof and combinations thereof, and (ii) at        least one modifier selected from the group of metal oxides        including the metals Bi, In, Mg, P, Sb, Zr, Group 1-3 metals,        lanthanide metals and combinations thereof, in combination with        or without (iii) at least one metal oxide including the metals        Cd, Co, Cr, Cu, Fe, Mn, Ni, Nb, Ta, V, Zn, binary combinations        thereof, ternary combinations thereof and higher combinations        thereof, the first catalyst layer cumulatively effective for        converting the alkene to its corresponding saturated carboxylic        acid and unsaturated carboxylic acid wherein the catalysts of        the first layer are impregnated on a metal oxide support; and    -   (c) a third catalyst layer cumulatively effective for converting        the saturated carboxylic acid and unsaturated carboxylic acid to        its corresponding saturated higher analogue unsaturated        carboxylic in the presence of an aldehyde, its corresponding        ester of an unsaturated carboxylic acid in the presence of an        alcohol and its corresponding higher analogue ester of an        unsaturated carboxylic acid in the presence of both formaldehyde        and an alcohol.

According to one embodiment the second catalyst layer comprises one ormore superacids and is self supporting or optionally impregnated on ametal oxide support and is oriented downstream from the second catalystlayer to increase the overall yield of corresponding ester of anunsaturated carboxylic acid, higher analogue unsaturated carboxylic acidand ester thereof.

According to one embodiment, additional feeds are incorporated (alsoreferred to a staging) including alkenes, oxygen, formaldehyde andalcohols for preparing unsaturated carboxylic acids, esters ofunsaturated carboxylic acids and their respective higher analogues usingthe catalyst system. Staging formaldehyde between the two catalystlayers produces the corresponding higher analogue unsaturated carboxylicacid (C_(n)+C₁). For example, the first catalyst converts propane (C₃alkane) to propionic acid (C₃ saturated carboxylic acid) and the secondcatalyst converts propionic acid to a higher analogue methacrylic acid(C₄ unsaturated carboxylic acid) in the presence of formaldehyde.

According to a separate embodiment, sparging formaldehyde and staging analcohol between the two catalyst beds produces the corresponding higheranalogue ester of unsaturated carboxylic acid. For example, the firstcatalyst converts propane (C₃) to propionic acid (C₃) and the secondcatalyst converts propionic acid (C₃) to methyl methacrylate (C₄) in thepresence of formaldehyde and methanol.

The invention provides a multi-stage method for preparing alkenes fromcorresponding alkanes, the process comprising the steps of:

-   -   (a) combining 5-30% by weight of a gaseous alkane, and a        stoichiometric amount of molecular oxygen, fully oxidizing the        alkane to carbon dioxide and water vapor in the form of steam;    -   (b) combining the steam and the remaining amount of alkane with        the steam and carbon dioxide and directing it to contact one or        more stem cracking catalysts;    -   (c) combining the gaseous mixture generated from (b) and        molecular oxygen to a short contact time reactor, the reactor        including a catalyst system comprising (a) at least one metal        selected from the group consisting of Ag, Au, Ir, Ni, Pd, Pt,        Rh, Ru, alloys thereof and combinations thereof; and (b) at        least one modifier selected from the group of metal oxides        including the metals Bi, In, Mg, P, Sb, Zr, Group 1-3 metals,        lanthanide metals and combinations thereof, the catalyst system        cumulatively effective at converting the gaseous alkane to its        corresponding gaseous alkene;        wherein the reactor is operated at a temperature of from 700° C.        to 1000° C., with a reactor residence time of no greater than        100 milliseconds.

The invention provides a multi-stage process for preparing unsaturatedcarboxylic acids from corresponding alkanes, the process comprising thesteps of:

-   -   (a) passing 5-30% by weight of a gaseous alkane, and a        stoichiometric amount of molecular oxygen, fully oxidizing the        alkane to carbon dioxide and water vapor in the form of steam;    -   (b) combining the steam and the remaining amount of alkane with        the steam and carbon dioxide and directing it to contact one or        more steam cracking catalysts; and    -   (c) catalytically converting the corresponding alkene generated        from (b) and molecular oxygen to a short contact time reactor,        the reactor including a mixed catalyst bed comprising (1) a        first catalyst layer comprising (i) at least one metal selected        from the group consisting of Ag, Au, Ir, Ni, Pd, Pt, Rh, Ru,        alloys thereof and combinations thereof; and (ii) at least one        modifier selected from the group of metal oxides including the        metals Bi, In, Mg, P, Sb, Zr, Group 1-3 metals, lanthanide        metals and combinations thereof, in combination with or        without (iii) at least one metal oxide including the metals Cd,        Co, Cr, Cu, Fe, Mn, Ni, Nb, Ta, V, Zn, binary combinations        thereof, ternary combinations thereof and higher combinations        thereof, wherein the catalysts of the first layer are        impregnated on a metal oxide support; and (2) a second catalyst        layer comprising at least one metal oxide including the metals        Mo, Fe, P, V and combinations thereof, the mixed bed catalyst        cumulatively effective at converting the gaseous alkene to its        corresponding gaseous unsaturated carboxylic acid;

wherein the second catalyst layer is separated at a distance downstreamfrom the first catalyst layer and the reactor is operated at atemperature of from 500° C. to 1000° C., with a reactor residence timeof no greater than 100 milliseconds; and wherein the one or morecracking catalysts is separated at a distance upstream from the shortcontact time reactor.

As a separate embodiment, the present invention provides a multi-stageprocess for preparing unsaturated carboxylic acids from correspondingalkanes, the process comprising the steps of

-   -   (a) passing 5-30% by weight of a gaseous alkane, and a        stoichiometric amount of molecular oxygen, fully oxidizing the        alkane to carbon dioxide and water vapor in the form of steam;    -   (b) combining the steam and the remaining amount of alkane with        the steam and carbon dioxide and directing it to contact one or        more steam cracking catalysts;    -   (c) catalytically converting the corresponding alkene generated        from (b) and molecular oxygen to a short contact time reactor,        the reactor including a mixed catalyst bed comprising at least        one catalytic zone, a first catalytic zone further        comprising: (1) at least one metal selected from the group        consisting of Ag, Au, Ir, Ni, Pd, Pt, Rh, Ru, alloys thereof and        combinations thereof, and (2) at least one modifier selected        from the group of metal oxides including the metals Bi, In, Mg,        P, Sb, Zr, Group 1-3 metals, lanthanide metals and combinations        thereof, in combination with or without (3) at least one metal        oxide including the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Nb, Ta,        V, Zn, binary combinations thereof, ternary combinations thereof        and higher combinations thereof, the catalyst converting the        corresponding gaseous alkene to a gaseous stream including a        corresponding gaseous unsaturated carboxylic acid and saturated        carboxylic acid; and    -   (d) passing the gaseous stream on to a second catalyst zone        including a catalyst impregnated on a metal oxide support, the        catalyst comprising at least one metal oxide including the        metals Mo, Fe, P, V and combinations thereof, the catalyst zones        cumulatively effective at converting the gaseous saturated        carboxylic acids to its corresponding gaseous unsaturated        carboxylic acid;        wherein the one or more cracking catalysts is separated at a        distance upstream relative to the direction of flow of the        gaseous stream to the first and second catalyst zones comprising        the short contact time reactor;

the first catalyst zone being disposed upstream of the second catalystzone relative to the direction of flow of the gaseous stream through thereactor;

the first catalyst zone being operated at a temperature of from 500° C.to 1000° C., with a first reaction zone residence time of no greaterthan 100 milliseconds;

the second catalyst zone being operated at a temperature of from 300° C.to 400° C., with a second reaction zone residence time of no greaterthan 100 milliseconds;

wherein the gaseous stream of the alkene is passed through the reactorin a single pass or wherein any unreacted alkene is recycled back intothe gaseous stream of alkene entering the reactor and wherein anysaturated carboxylic acid is recycled back into the second catalyst zoneto increase the overall yield of unsaturated carboxylic acid.

The invention also provides a multi-stage process for converting alkanesto their corresponding esters of unsaturated carboxylic acids, theprocess comprising the steps of:

-   -   (a) passing 5-30% by weight of a gaseous alkane, and a        stoichiometric amount of molecular oxygen, fully oxidizing the        alkane to carbon dioxide and water vapor in the form of steam;    -   (b) combining the steam and the remaining amount of alkane with        the steam and carbon dioxide and directing it to contact one or        more steam cracking catalysts; and    -   (c) catalytically converting the corresponding alkene generated        from (b) and molecular oxygen to a short contact time reactor,        the reactor including a mixed catalyst bed comprising (1) a        first catalyst layer comprising (i) at least one metal selected        from the group consisting of Ag, Au, Ir, Ni, Pd, Pt, Rh, Ru,        alloys thereof and combinations thereof; and (ii) at least one        modifier selected from the group of metal oxides including the        metals Bi, In, Mg, P, Sb, Zr, Group 1-3 metals, lanthanide        metals and combinations thereof, in combination with or        without (iii) at least one metal oxide including the metals Cd,        Co, Cr, Cu, Fe, Mn, Ni, Nb, Ta, V, Zn, binary combinations        thereof, ternary combinations thereof and higher combinations        thereof, the first catalyst layer cumulatively effective at        converting the gaseous alkane to its corresponding gaseous        unsaturated carboxylic acid; wherein the catalysts of the first        layer are impregnated on a metal oxide support; and (2) a second        catalyst layer comprising one or more catalysts cumulatively        effective at converting the gaseous unsaturated carboxylic acid        to its corresponding gaseous ester;

wherein the second catalyst layer is separated at a distance downstreamfrom the first catalyst layer and the reactor is operated at atemperature of from 500° C. to 1000° C., with a reactor residence timeof no greater than 100 milliseconds; and wherein the one or morecracking catalysts is separated at a distance upstream relative to theflow of the gaseous stream of reactants to the short contact timereactor.

According to one embodiment, an additional catalyst layer is includedbetween the first and second layers comprising at least one metal oxideincluding the metals Mo, Fe, P, V and combinations thereof, the catalystadditional layer cumulatively effective at converting the gaseoussaturated carboxylic acid to its corresponding gaseous unsaturatedcarboxylic acid.

The invention also provides a multi-stage process for converting alkanesto their corresponding esters of unsaturated carboxylic acids, theprocess comprising the steps of:

-   -   (a) passing 5-30% by weight of a gaseous alkane, and a        stoichiometric amount of molecular oxygen, fully oxidizing the        alkane to carbon dioxide and water vapor in the form of steam;    -   (b) combining the steam and the remaining amount of alkane with        the steam and carbon dioxide and directing it to contact one or        more steam cracking catalysts;    -   (c) catalytically converting the corresponding alkene generated        from (b) and molecular oxygen to a short contact time reactor,        the reactor including a mixed catalyst bed comprising at least        one catalytic zone, a first catalytic zone further        comprising: (1) at least one metal selected from the group        consisting of Ag, Au, Ir, Ni, Pd, Pt, Rh, Ru, alloys thereof and        combinations thereof, and (2) at least one modifier selected        from the group of metal oxides including the metals Bi, In, Mg,        P, Sb, Zr, Group 1-3 metals, lanthanide metals and combinations        thereof, in combination with or without (3) at least one metal        oxide including the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Nb, Ta,        V, Zn, binary combinations thereof, ternary combinations thereof        and higher combinations thereof, the catalyst converting the        corresponding gaseous alkene to a gaseous stream including a        corresponding gaseous unsaturated carboxylic acid and saturated        carboxylic acid;    -   (d) passing the gaseous stream on to a second catalyst zone        including a catalyst impregnated on a metal oxide support, the        catalyst comprising at least one metal oxide including the        metals Mo, Fe, P, V and combinations thereof, the catalyst zones        cumulatively effective at converting the gaseous saturated        carboxylic acids to its corresponding gaseous unsaturated        carboxylic acid; and    -   (e) passing a second gaseous stream comprising an alcohol to the        reactor;

wherein the one or more cracking catalysts is separated at a distanceupstream relative to the direction of flow of the gaseous stream to thefirst and second catalysts in first and second reaction zones comprisingthe short contact time reactor; the reactor containing one or moreoxidation catalysts cumulatively effective for converting the alkene toan ester of its corresponding unsaturated carboxylic acid with thealcohol;

the one or more oxidation catalysts comprising a first catalyst systemeffective for converting the alkane to its corresponding unsaturatedcarboxylic acid and a second catalyst effective for converting theethylenically unsaturated alcohol, in the presence of the alcohol, to anester of its corresponding ethylenically unsaturated carboxylic acidwith the alcohol;

the first catalyst being disposed in a first reaction zone;

the second catalyst being disposed in a second reaction zone;

the first reaction zone being disposed upstream of the second reactionzone relative to the direction of flow of the first gaseous streamthrough the reactor;

the second gaseous stream being fed to the reactor intermediate thefirst reaction zone and the second reaction zone;

the first reaction zone being operated at a temperature of from 500° C.to 1000° C., with a first reaction zone residence time of no greaterthan 100 milliseconds;

the second reaction zone being operated at a temperature of from 300° C.to 400° C., with a second reaction zone residence time of no greaterthan 100 milliseconds.

The invention also provides a multi-stage process for the production ofhigher unsaturated carboxylic acids, the process comprising the stepsof;

-   -   (a) passing 5-30% by weight of a gaseous alkane, and a        stoichiometric amount of molecular oxygen, fully oxidizing the        alkane to carbon dioxide and water vapor in the form of steam;    -   (b) combining the steam and the remaining amount of alkane with        the steam and carbon dioxide and directing it to contact one or        more steam cracking catalysts;    -   (c) catalytically converting the corresponding alkene generated        from (b) and molecular oxygen to a short contact time reactor,        the reactor including a mixed catalyst bed comprising at least        one catalytic zone, a first catalytic zone further        comprising: (1) at least one metal selected from the group        consisting of Ag, Au, Ir, Ni, Pd, Pt, Rh, Ru, alloys thereof and        combinations thereof; and (2) at least one modifier selected        from the group of metal oxides including the metals Bi, In, Mg,        P, Sb, Zr, Group 1-3 metals, lanthanide metals and combinations        thereof, in combination with or without (3) at least one metal        oxide including the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Nb, Ta,        V, Zn, binary combinations thereof, ternary combinations thereof        and higher combinations thereof, the catalyst converting the        corresponding gaseous alkene to a gaseous stream including a        corresponding gaseous unsaturated carboxylic acid and saturated        carboxylic acid;    -   (d) passing the gaseous stream on to a second catalyst zone        including a catalyst impregnated on a metal oxide support, the        catalyst comprising at least one metal oxide including the        metals Mo, Fe, P, V and combinations thereof, the catalyst zones        cumulatively effective at converting the gaseous saturated        carboxylic acids to its corresponding gaseous unsaturated        carboxylic acid;    -   (e) passing a first gaseous stream comprising an alkane and        molecular oxygen to a reactor; and    -   (f) passing a second gaseous stream comprising an aldehyde to        the reactor;

wherein the one or more cracking catalysts is separated at a distanceupstream relative to the direction of flow of the gaseous stream to thefirst and second catalysts in first and second reaction zones comprisingthe short contact time reactor; the reactor containing one or moreoxidation catalysts cumulatively effective for converting the alkane toits corresponding higher analogue of an unsaturated carboxylic acid;

the one or more oxidation catalysts comprising a first catalyst systemeffective for converting the alkane to its corresponding saturatedcarboxylic acid and a second catalyst effective for converting thesaturated carboxylic acid, in the presence of the aldehyde, to itscorresponding higher analogue unsaturated carboxylic acid with thealdehyde;

the first catalyst being disposed in a first reaction zone;

the second catalyst being disposed in a second reaction zone;

the first reaction zone being disposed upstream of the second reactionzone relative to the direction of flow of the first gaseous streamthrough the reactor;

the second gaseous stream being fed to the reactor intermediate thefirst reaction zone and the second reaction zone;

the first reaction zone being operated at a temperature of from 500° C.to 1000° C., with a first reaction zone residence time of no greaterthan 100 milliseconds;

the second reaction zone being operated at a temperature of from 300° C.to 400° C., with a second reaction zone residence time of no greaterthan 100 milliseconds.

The invention also provides a multi-stage process for an alkane to itscorresponding unsaturated carboxylic acids, the process comprising thesteps of:

-   -   (a) passing 5-30% by weight of a gaseous alkane, and a        stoichiometric amount of molecular oxygen, fully oxidizing the        alkane to carbon dioxide and water vapor in the form of steam;    -   (b) combining the steam and the remaining amount of alkane with        the steam and carbon dioxide and directing it to contact one or        more steam cracking catalysts;    -   (c) catalytically converting the corresponding alkene generated        from (b) and molecular oxygen to a short contact time reactor,        the reactor including a mixed catalyst bed comprising at least        one catalytic zone, a first catalytic zone further        comprising: (1) at least one metal selected from the group        consisting of Ag, Au, Ir, Ni, Pd, Pt, Rh, Ru, alloys thereof and        combinations thereof; and (2) at least one modifier selected        from the group of metal oxides including the metals Bi, In, Mg,        P, Sb, Zr, Group 1-3 metals, lanthanide metals and combinations        thereof, in combination with or without (3) at least one metal        oxide including the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Nb, Ta,        V, Zn, binary combinations thereof, ternary combinations thereof        and higher combinations thereof, the catalyst converting the        corresponding gaseous alkene to a gaseous stream including a        corresponding gaseous unsaturated carboxylic acid and saturated        carboxylic acid; and    -   (d) passing the gaseous stream on to a second catalyst zone        including a catalyst impregnated on a metal oxide support, the        catalyst comprising at least one metal oxide including the        metals Mo, Fe, P, V and combinations thereof, the catalyst zones        cumulatively effective at converting the gaseous saturated        carboxylic acids to its corresponding gaseous unsaturated        carboxylic acid;

wherein the one or more cracking catalysts is separated at a distanceupstream relative to the direction of flow of the gaseous stream to thefirst and second catalysts in first and second reaction zones comprisingthe short contact time reactor; the reactor containing one or moreoxidation catalysts cumulatively effective for converting the alkene toits corresponding unsaturated carboxylic acid;

the one or more oxidation catalysts comprising at least one steamcracking catalyst effective for converting the alkane to itscorresponding alkene, a first and second catalyst effective for thealkene to its corresponding saturated carboxylic acid and unsaturatedcarboxylic acid, and a third catalyst effective for converting thesaturated carboxylic acid to its corresponding unsaturated carboxylicacid;

the first catalyst being disposed in a first reaction zone;

the second catalyst being disposed in a second reaction zone;

the third catalyst being disposed in a third reaction zone;

the first reaction zone being disposed upstream of the second reactionzone relative to the direction of flow of the first gaseous streamthrough the reactor;

the second reaction zone being disposed upstream of the third reactionzone relative to the direction of flow of the first gaseous streamthrough the reactor;

the second gaseous stream being fed to the reactor intermediate thesecond reaction zone and the third reaction zone;

the first reaction zone being operated at a temperature of from 500° C.to 1000° C., with first reaction zone residence time of no greater than100 milliseconds;

the second reaction zone being operated at a temperature of from 300° C.to 400° C., with a second reaction zone residence time of no greaterthan 100 milliseconds;

the third reaction zone being operated at a temperature of from 100° C.to 300° C., with a third reaction zone residence time of no greater than100 milliseconds.

The invention provides a multi-stage process for converting an alkane toa corresponding higher analogue unsaturated carboxylic acids, theprocess comprising the steps of:

-   -   (a) passing 5-30% by weight of a gaseous alkane, and a        stoichiometric amount of molecular oxygen, fully oxidizing the        alkane to carbon dioxide and water vapor in the form of steam;    -   (b) combining the steam and the remaining amount of alkane with        the steam and carbon dioxide and directing it to contact one or        more steam cracking catalysts;    -   (c) catalytically converting the corresponding alkene generated        from (b) and molecular oxygen to a short contact time reactor,        the reactor including a mixed catalyst bed comprising at least        one catalytic zone, a first catalytic zone further        comprising: (1) at least one metal selected from the group        consisting of Ag, Au, Ir, Ni, Pd, Pt, Rh, Ru, alloys thereof and        combinations thereof; and (2) at least one modifier selected        from the group of metal oxides including the metals Bi, In, Mg,        P, Sb, Zr, Group 1-3 metals, lanthanide metals and combinations        thereof, in combination with or without (3) at least one metal        oxide including the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Nb, Ta,        V, Zn, binary combinations thereof, ternary combinations thereof        and higher combinations thereof, the catalyst converting the        corresponding gaseous alkene to a gaseous stream including a        corresponding gaseous unsaturated carboxylic acid and saturated        carboxylic acid; and    -   (d) passing the gaseous stream on to a second catalyst zone        including a catalyst impregnated on a metal oxide support, the        catalyst comprising at least one metal oxide including the        metals Mo, Fe, P, V and combinations thereof, the catalyst zones        cumulatively effective at converting the gaseous saturated        carboxylic acids to its corresponding gaseous unsaturated        carboxylic acid; and    -   (e) passing a second gaseous stream comprising an aldehyde to        the reactor;

wherein the one or more cracking catalysts is separated at a distanceupstream relative to the direction of flow of the gaseous stream to thefirst and second catalysts in first and second reaction zones comprisingthe short contact time reactor;

the reactor containing one or more oxidation catalysts cumulativelyeffective for the oxidation of the alkane to its correspondingunsaturated carboxylic acid with the aldehyde;

the one or more oxidation catalysts comprising a first catalysteffective for converting the alkane to its corresponding alkene, asecond catalyst effective for converting the alkene to its correspondingsaturated carboxylic acid, and a third catalyst effective for convertingthe saturated carboxylic acid, in the presence of an aldehyde, to itscorresponding higher analogue unsaturated carboxylic acid with thealdehyde;

the first catalyst being disposed in a first reaction zone;

the second catalyst being disposed in a second reaction zone;

the third catalyst being disposed in a third reaction zone;

the first reaction zone being disposed upstream of the second reactionzone relative to the direction of flow of the first gaseous streamthrough the reactor;

the second reaction zone being disposed upstream of the third reactionzone relative to the direction of flow of the first gaseous streamthrough the reactor;

the second gaseous stream being fed to the reactor intermediate thesecond reaction zone and the third reaction zone;

the first reaction zone being operated at a temperature of from 500° C.to 1000° C., with first reaction zone residence time of no greater than100 milliseconds;

the second reaction zone being operated at a temperature of from 300° C.to 400° C., with a second reaction zone residence time of no greaterthan 100 milliseconds;

the third reaction zone being operated at a temperature of from 100° C.to 300° C., with a third reaction zone residence time of no greater than100 milliseconds.

The invention provides a multi-stage process for converting an alkane toa corresponding higher analogue ester of an unsaturated carboxylicacids, the process comprising the steps of:

-   -   (a) passing 5-30% by weight of a gaseous alkane, and a        stoichiometric amount of molecular oxygen, fully oxidizing the        alkane to carbon dioxide and water vapor in the form of steam;    -   (b) combining the steam and the remaining amount of alkane with        the steam and carbon dioxide and directing it to contact one or        more steam cracking catalysts;    -   (c) catalytically converting the corresponding alkene generated        from (b) and molecular oxygen to a short contact time reactor,        the reactor including a mixed catalyst bed comprising at least        one catalytic zone, a first catalytic zone further        comprising: (1) at least one metal selected from the group        consisting of Ag, Au, Ir, Ni, Pd, Pt, Rh, Ru, alloys thereof and        combinations thereof; and (2) at least one modifier selected        from the group of metal oxides including the metals Bi, In, Mg,        P, Sb, Zr, Group 1-3 metals, lanthanide metals and combinations        thereof, in combination with or without (3) at least one metal        oxide including the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Nb, Ta,        V, Zn, binary combinations thereof, ternary combinations thereof        and higher combinations thereof, the catalyst converting the        corresponding gaseous alkene to a gaseous stream including a        corresponding gaseous unsaturated carboxylic acid and saturated        carboxylic acid;    -   (d) passing the gaseous stream on to a second catalyst zone        including a catalyst impregnated on a metal oxide support, the        catalyst comprising at least one metal oxide including the        metals Mo, Fe, P, V and combinations thereof, the catalyst zones        cumulatively effective at converting the gaseous saturated        carboxylic acids to its corresponding gaseous unsaturated        carboxylic acid;    -   (e) passing a second gaseous stream comprising an aldehyde        including formaldehyde to the reactor; and    -   (f) passing a third gaseous stream comprising an alcohol to the        reactor;

the reactor containing one or more oxidation catalysts cumulativelyeffective for converting the alkane to its corresponding higher analogueester of an unsaturated carboxylic acid with the aldehyde and thealcohol;

the one or more oxidation catalysts comprising a first catalyst systemeffective for converting the alkane to its corresponding saturatedcarboxylic acid, a second catalyst effective for converting thesaturated carboxylic acid, in the presence of the aldehyde, to itscorresponding higher analogue unsaturated carboxylic acid, and a thirdcatalyst effective for converting the higher analogue unsaturatedcarboxylic acid, in the presence of the alcohol, to an higher analogueester of its corresponding unsaturated carboxylic acid with the alcohol;

the first catalyst system being disposed in a first reaction zone;

the second catalyst being disposed in a second reaction zone;

the third catalyst being disposed in a third reaction zone;

wherein the one or more cracking catalysts is separated at a distanceupstream relative to the direction of flow of the gaseous stream to thefirst and second catalysts in first and second reaction zones comprisingthe short contact time reactor;

the first reaction zone being disposed upstream of the second reactionzone relative to the direction of flow of the first gaseous streamthrough the reactor;

the second reaction zone being disposed upstream of the third reactionzone relative to the direction of flow of the first gaseous streamthrough the reactor; the second gaseous stream being fed to the reactorintermediate the first reaction zone and the second reaction zone; thethird gaseous stream being fed to the reactor intermediate the secondreaction zone and the third reaction zone;

the first reaction zone being operated at a temperature of from500° C.to 1000° C., with first reaction zone residence time of no greater than100 milliseconds;

the second reaction zone being operated at a temperature of from 300° C.to 400° C., with a second reaction zone residence time of no greaterthan 100 milliseconds;

the third reaction zone being operated at a temperature of from 100° C.to 300° C., with a third reaction zone residence time of no greater than100 milliseconds.

The invention also provides a multi-stage recycle process comprising thesteps of: (a) converting an alkane to its corresponding productsselected from alkene using one or more steam cracking catalysts, (b)converting the corresponding alkene to further oxygenated productsselected from unsaturated carboxylic acid, and higher analogueunsaturated carboxylic acid in a short contact time reactor using thecatalyst systems of the invention; and (c) adding the resulting productor products to the front end of a second fixed bed oxidation reactorunder short contact time conditions with the product(s) from the firststeam cracking reactor acting as feed to the second reactor. Accordingto one embodiment this includes feeding any unreacted alkane from thefirst steam cracking reactor and any unreacted alkene from the shortcontact time reactor to the short contact time reactor reactor torecycle the respective alkane and alkene.

The invention also provides a multi-stage process for converting analkane to its corresponding products selected from unsaturatedcarboxylic acid, higher analogue unsaturated carboxylic acid and esterthereof comprising the step of providing a thermal gradient having thecumulative effect of improving conversion of the alkane to a desiredoxygenated product.

The invention also provides a multi-stage process for converting analkane to its corresponding products selected from unsaturatedcarboxylic acid, higher analogue unsaturated carboxylic acid and esterthereof comprising the step of providing a catalytic cascade furthercomprising one or more catalytic systems having the cumulative effect ofimproving conversion of the alkane to a desired oxygenated product.

As used herein the term “multi-stage process” refers to a combination oftwo or more stages including two or more reactors, each reactorcomprising at least one catalyst, the reactors further comprising acombination of at least one catalytic reactor with at least one catalystin a short contact time reactor which effects the cumulative conversionof one or more alkanes to one or more corresponding oxygenated products.According to one embodiment the multi-stage process comprises a steamcracking reactor in combination with at least one catalyst in a shortcontact time reactor, the steam cracking reactor converting one or morealkanes to one or more corresponding alkenes and the shorts contact timereactor converting the corresponding one or more alkenes to one or morefurther corresponding oxygenated products.

As used herein, the term “cumulatively converting” refers producing adesired product stream from one or more specific reactants usingcatalyst systems of the invention under specific reaction conditions. Asan illustrative example, cumulatively converting an alkane to an esterof its corresponding unsaturated carboxylic acid with an alcohol meansthat the catalyst(s) utilized will produce a product stream comprisingan ester of the added alcohol with the unsaturated carboxylic acidcorresponding to the added alkane when acting on a feed stream(s)comprising the alkane and the alcohol under the designated reactionconditions.

As used herein the term “catalytic system” refers to two or morecatalysts. The term “multi-stage catalytic system” refers to one or moresteam cracking catalysts in combination with one or more oxidationcatalysts for cumulatively converting alkenes to correspondingoxygenated products. For example, platinum metal and indium oxideimpregnated on an alumina support defines a catalytic system. Anotherexample is niobium oxide impregnated on platinum gauze. Yet anotherexample is palladium metal, vanadium oxide and magnesium oxideimpregnated on silica.

Accordingly, the present invention relates to multi-stagedoxidation/dehydrogenation catalysts and multi-stage processes forpreparing dehydrogenated products and oxygenated products from alkanesand oxygen at short contact times. Suitable alkanes include alkaneshaving straight or branched chains. Examples of suitable alkanes includeC₃-C₂₅ alkanes, preferably C₃-C₈ alkanes such as propane, butane,isobutane, pentane, isopentane, hexane and heptane. Particularlypreferred alkanes are propane and isobutane.

Multi-staged catalyst systems of the invention cumulatively convertalkanes to their corresponding alkenes and oxygenates includingsaturated carboxylic acids, unsaturated carboxylic acids, estersthereof, and higher analogue unsaturated carboxylic acids and estersthereof. The catalytic systems are designed to provide a specificalkene, oxygenate and combinations thereof. According to one embodiment,use of one or more conventional steam cracking catalysts, alkanes arecatalytically converted to corresponding alkenes. The correspondingalkenes produced in the cracking reactor are directed to one or moreoxidation catalysts in a short contact reactor to provide correspondingoxygenated products. According to a separate embodiment, any unreactedalkane, alkene or intermediate is recycled to catalytically convert itto its corresponding oxygenate in accordance with the invention.According to a separate embodiment, alkenes produced fromdehydrogenation of corresponding alkanes using steam cracking catalystsor catalytic systems of the invention are deliberately produced asin-process chemical intermediates and not isolated as correspondingalkenes before selective partial oxidation to further correspondingoxygenated products. For example, when catalytically converting analkane to its corresponding ethylenically unsaturated carboxylic acid,any unreacted alkene produced is recovered or recycled to catalyticallyconvert it to its corresponding ethylenically unsaturated carboxylicacid product stream.

According to one embodiment, the alkane is also catalytically convertedto its corresponding alkene intermediates through two or more steamcracking catalytic zones. For example, propane is converted to propylenethrough a steam cracking reactor. According to a separate embodiment, analkane is catalytically converted to its corresponding saturatedcarboxylic acid in a first and second stage catalytic zone or layer of amixed hybrid catalyst bed. The saturated carboxylic acid, in thepresence of an additional formaldehyde stream, to its correspondinghigher analogue ethylenically unsaturated carboxylic acid in a secondcatalytic zone or layer of a mixed bed catalyst. In a specific example,propane is catalytically converted to propionic acid and the propionicacid in the presence of formaldehyde is catalytically converted tomethacrylic acid.

As used herein, the term “higher analogue unsaturated carboxylic acid”and “ester of a higher analogue unsaturated carboxylic acid” refer toproducts having at least one additional carbon atom in the final productas compared to the alkane or alkene reactants. For example given above,propane (C₃ alkane) is converted to propionic acid (C₃ saturatedcarboxylic acid), which in the presence of formaldehyde is converted toits corresponding higher analogue (C₄) carboxylic acid, methacrylic acidusing catalysts of the invention.

Suitable alkenes used in the invention include alkenes having straightor branched chains. Examples of suitable alkenes include C₃-C₂₅ alkenes,preferably C₃-C₈ alkenes such as propene (propylene),1-butene(butylene), 2-methylpropene(isobutylene), 1-pentene and1-hexene. Particularly preferred alkenes are propylene and isobutylene.

Suitable aldehydes used in the invention include for exampleformaldehyde, ethanal, propanal and butanal.

Steam cracking catalyst systems of the invention convert alkanes totheir corresponding alkenes. Oxidation catalyst systems convertcorresponding alkenes to further corresponding oxygenates includingunsaturated and saturated carboxylic acids having straight or branchedchains. Multi-staged catalyst systems cumulatively convert correspondingalkanes to corresponding alkenes and further corresponding oxygenatesincluding but not limited to unsaturated and saturated carboxylic acidshaving straight or branched chains. Examples include C₃-C₈ saturatedcarboxylic acids such as propionic acid, butanoic acid, isobutyric acid,pentanoic acid and hexanoic acid. According to one embodiment, saturatedcarboxylic acids produced from corresponding alkanes using catalystsystems of the invention are deliberately produced as in-processchemical intermediates and not isolated before selective partialoxidation to oxygenated products including unsaturated carboxylic acids,esters of unsaturated carboxylic acids, and higher esters of unsaturatedcarboxylic acids. According to a separate embodiment, any saturatedcarboxylic acid produced is converted using catalysts of the inventionto its corresponding product stream including an ethylenicallyunsaturated carboxylic acid, esters thereof, a higher analogueunsaturated carboxylic acid or esters thereof.

According to one embodiment, certain oxidation catalyst systemscumulatively covert alkenes to their corresponding oxygenated productsand multi-staged catalyst systems of the invention cumulatively convertalkanes to their corresponding ethylenically unsaturated carboxylicacids and higher analogues having straight or branched chains. Examplesinclude C₃-C₈ ethylenically unsaturated carboxylic acids such as acrylicacid, methacrylic acid, butenoic acid, pentenoic acid, hexenoic acid,maleic acid, and crotonic acid. Higher analogue ethylenicallyunsaturated carboxylic acids are prepared from corresponding alkanes andaldehydes. For example, methacrylic acid is prepared from propane andformaldehyde. According to a separate embodiment, the corresponding acidanhydrides are also produced when preparing ethylenically unsaturatedcarboxylic acids from their respective alkanes. The catalysts of theinvention are usefully employed to convert propane to acrylic acid andits higher unsaturated carboxylic acid methacrylic acid and to convertisobutane to methacrylic acid.

According to one embodiment, certain oxidation catalyst systems of theinvention are also advantageously utilized converting alkenes to theircorresponding esters of unsaturated carboxylic acids and higheranalogues and multi-staged catalyst systems of the invention are alsoadvantageously utilized for cumulatively converting alkenes to theircorresponding esters of unsaturated carboxylic acids and higheranalogues. Specifically, these esters include, but are not limited to,butyl acrylate from butyl alcohol and propane, β-hydroxyethyl acrylatefrom ethylene glycol and propane, methyl methacrylate from methanol andisobutane, butyl methacrylate from butyl alcohol and isobutane,β-hydroxyethyl methacrylate from ethylene glycol and isobutane, andmethyl methacrylate from propane, formaldehyde and methanol.

In addition to these esters, other esters are formed through thisinvention by varying the type of alcohol introduced into the reactorand/or the alkane, alkene and corresponding oxygenates introduced intothe reactor.

Suitable alcohols include monohydric alcohols, dihydric alcohols andpolyhydric alcohols. Of the monohydric alcohols reference may be made,without limitation, to C₁-C₂₀ alcohols, preferably C₁-C₆ alcohols, mostpreferably C₁-C₄ alcohols. The monohydric alcohols may be aromatic,aliphatic or alicyclic; straight or branched chain; saturated orunsaturated; and primary, secondary or tertiary. Particularly preferredmonohydric alcohols include methyl alcohol, ethyl alcohol, propylalcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol and tertiarybutyl alcohol. Of the dihydric alcohols reference may be made, withoutlimitation, to C₂-C₆ diols, preferably C₂-C₄ diols. The dihydricalcohols may be aliphatic or alicyclic; straight or branched chain; andprimary, secondary or tertiary. Particularly preferred dihydric alcoholsinclude ethylene glycol (1,2-ethanediol), propylene glycol(1,2-propanediol), trimethylene glycol (1,3-propanediol), 1,2-butanedioland 2,3-butanediol. Of the polyhydric alcohols reference will only bemade to glycerol (1,2,3-propanetriol).

The unsaturated carboxylic acid corresponding to the added alkane is theα,β-unsaturated carboxylic acid having the same number of carbon atomsas the starting alkane and the same carbon chain structure as thestarting alkane, e.g., acrylic acid is the unsaturated carboxylic acidcorresponding to propane and methacrylic acid is the unsaturatedcarboxylic acid corresponding to isobutane.

Similarly, the unsaturated carboxylic acid corresponding to an alkene isthe α,β-unsaturated carboxylic acid having the same number of carbonatoms as the alkene and the same carbon chain structure as the alkene,e.g., acrylic acid is the unsaturated carboxylic acid corresponding topropene and methacrylic acid is the unsaturated carboxylic acidcorresponding to isobutene.

Likewise, the unsaturated carboxylic acid corresponding to anunsaturated aldehyde is the α,β-unsaturated carboxylic acid having thesame number of carbon atoms as the unsaturated aldehyde and the samecarbon chain structure as the unsaturated aldehyde, e.g., acrylic acidis the unsaturated carboxylic acid corresponding to acrolein andmethacrylic acid is the unsaturated carboxylic acid corresponding tomethacrolein.

The alkene corresponding to the added alkane is the alkene having thesame number of carbon atoms as the starting alkane and the same carbonchain structure as the starting alkane, e.g., propene is the alkenecorresponding to propane and isobutene is the alkene corresponding toisobutane. (For alkenes having four or more carbon atoms, the doublebond is in the 2-position of the carbon-carbon chain of the alkene.)

The unsaturated aldehyde corresponding to the added alkane is thea,13-unsaturated aldehyde having the same number of carbon atoms as thestarting alkane and the same carbon chain structure as the startingalkane, e.g., acrolein is the unsaturated aldehyde corresponding topropane and methacrolein is the unsaturated carboxylic acidcorresponding to isobutane.

Similarly, the unsaturated aldehyde corresponding to an alkene is theα,β-unsaturated carboxylic acid having the same number of carbon atomsas the alkene and the same carbon chain structure as the alkene, e.g.,acrolein is the unsaturated aldehyde corresponding to propene andmethacrolein is the unsaturated aldehyde corresponding to isobutene.

With respect to the metals used in the catalysts of the inventions, thefollowing definitions based on the Periodic Table apply:

-   -   Group 1 comprises Li, Na, K, Rb and Cs.    -   Group 2 comprises Mg, Ca, Sr and Ba.    -   Group 3 comprises B, Al, Ga, In and Tl.    -   Lanthanides comprises Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb,        Dy, Ho, Er, Tm, Yb, Lu and all stable elements of the actinide        series.    -   Group 4A comprises C, Si, Ge, Sn and Pb.    -   Group 4B comprises Ti, Zr and Hf.    -   Group 5A comprises N, P, As, Sb and Bi.    -   Group 5B comprises V, Nb and Ta.    -   Group 6B comprises Cr, Mo and W.    -   Group 7B comprises Mn, Tc and Re.    -   Group 8 comprises Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt.

Accordingly, the present invention provides a supported catalyst systemfor converting alkanes to their corresponding alkenes under steamcracking conditions and for converting alkenes to correspondingoxygenates at short contact times.

The support structure is three-dimensional, i.e. the support hasdimensions along an x, y and z orthogonal axes of a Cartesian coordinatesystem, and affords a relatively high surface area per unit volume.Though lower and higher amounts are possible, in one embodiment, thesupport structure exhibits a surface area of 0.01 to 50 m²/g, preferably0.1 to 10 m²/g.

Preferably, the support structure will have a porous structure andexhibit a pore volume percent ranging from 1 to 95%, more preferably 5to 80%, and still more preferably 10 to 50%. Thus, the support structurepermits relatively high feed velocities with insubstantial pressuredrop.

Further, the support structure is sufficiently strong so that it doesnot fracture under the weight of the catalyst, which can range up toalmost 100% of the weight of the combination of the catalyst and thesupport structure. More preferably, however, the support structure is atleast 60% of the weight of the combination. Still more preferably, it is70 to 99.99% of the weight of the combination. Even still morepreferably, the support structure is 90 to 99.9% of the weight of thecombination.

The exact physical form of the support structure is not particularlyimportant so long as it meets the above noted general criteria. Examplesof suitable physical forms include foam, honeycomb, lattice, mesh,monolith, woven fiber, non-woven fiber, gauze, perforated substrates(e.g., foil), particle compacts, fibrous mat and mixtures thereof. Forthese supports it will be appreciated that typically one or more opencells will be included in the structure. The cell size may vary asdesired, as may the cell density, cell surface area, open frontal areaand other corresponding dimensions. By way of example, one suchstructure has an open frontal area of at least 75%. The cell shape mayalso vary and may include polygonal shapes, circles, ellipses, as wellas others.

The support structure may be fabricated from a material that is inert tothe reaction environment of the catalytic reaction. Suitable materialsinclude ceramics and their isomorphs such as silica, alumina (includingα-, β- and γ-isomorphs), silica-alumina, aluminosilicate, zirconia,titania, boria, mullite, lithium aluminum silicate, oxide-bonded siliconcarbide, metal alloy monoliths, Fricker type metal alloys, FeCrAl alloysand mixtures thereof. (Alternatively, the catalyst may be prepared so asto define the support structure itself, e.g., by “green” compacting oranother suitable technique.)

The catalysts may be applied to the support structure using any suitableart-disclosed technique. For instance, the catalyst may be vapordeposited (e.g., by sputtering, plasma deposition or some other form ofvapor deposition). The catalyst may be impregnated or coated thereon(e.g., by wash coating a support with a solution, slurry, suspension ordispersion of catalyst). The support may be coated with a catalystpowder (i.e. powder coating). (Alternatively, where the supportstructure is the catalyst itself, a “green” body of catalyst may becompacted to yield the desired structure.)

The multi-staged catalyst system of the invention cumulatively convertsalkanes to their corresponding alkenes and oxygenates. The steamcracking catalyst comprises at least one steam cracking catalysts. Theoxidation catalyst under short contact times comprises three components:(a) at least one metal selected from the group consisting of Ag, Au, Ir,Ni, Pd, Pt, Rh, Ru, alloys thereof and combinations thereof; and (b) atleast one modifier selected from the group of metal oxides including themetals Bi, In, Mg, P, Sb, Zr, Group 1-3 metals, lanthanide metals andcombinations thereof, in combination with or without (c) at least onemetal oxide including the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Nb, Ta, V,Zn, binary combinations thereof, ternary combinations thereof and highercombinations thereof, wherein the catalysts are impregnated on a metaloxide support.

Catalytic component (a) is a promoter usefully employed to oxidativelydehydrogenate alkanes to their corresponding alkenes. The catalyst ispresent on the support in the form of finely dispersed metal particlesincluding alloys (microns to nanometers) having high surface area.Alternatively, the catalyst is in the form of a fine gauze, includingnanometer sized wires. The catalyst is impregnated on the support usingtechniques selected from metal sputtering, chemical vapor deposition,chemical and/or electrochemical reduction of the metal oxide.Combinations of promoters and their alloys are useful employed. Thecatalytic system component comprises metal oxides and metal oxides usedin combination with promoters.

Catalytic component (b) is a modifier usefully employed to partiallyoxidize alkanes to their corresponding saturated carboxylic acids andunsaturated carboxylic acids. Metal oxides catalysts are in the form ofbinary, ternary, quaternary or higher order mixed metal oxides. Thereducible metal oxide may be an oxide of a metal selected from the groupconsisting of Bi, In, Mg, P, Sb, Zr, Group 1-3 metals, Y, Sc, La, Zr,Ta, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and mixturesthereof. The modifier may preferably be present in an amount of from0.0001 to 10 wt % of the catalyst composition (promoter plus reduciblemetal oxide), more preferably from 0.001 to 5 wt % of the catalystcomposition, and still more preferably from 0.01 to 2 wt % of thecatalyst composition.

Catalytic component (c) is usefully employed to partially oxidizealkanes to their corresponding alkenes, saturated carboxylic acids andunsaturated carboxylic acids. Metal oxides catalysts are in the form ofbinary, ternary, quaternary or higher order mixed metal oxides. Thereducible metal oxide may be an oxide of a metal selected from the groupconsisting of Cu, Cd, Co, Cr Fe, V, Mn, Ni, Nb, Mo, W, Re, Ga, Ge, In,Sn, Sb, Tl, Pb, Bi, Te, As, Se, V, Zn, Y, Zr, Ta and mixtures thereof.Preferably, the reducible metal oxide is selected from the groupconsisting of metals Cd, Co, Cr, Cu, Fe, Mn, Ta, V and combinationsthereof and mixtures thereof. The promoter is a metal selected from Fe,Ru, Os, Co, Rh, Ir, Ni, Pd and Pt, preferably a metal selected from thegroup consisting of Pt, Pd, Rh, Ir, Ru and mixtures thereof. Thepromoter may preferably be present in an amount of from 0.0001 to 10 wt% of the catalyst composition (promoter plus reducible metal oxide),more preferably from 0.001 to 5 wt % of the catalyst composition, andstill more preferably from 0.01 to 2 wt % of the catalyst composition.The catalyst is present on the support in the form of finely dispersedmetal oxide particles (microns to nanometers) having high surface area.The catalytic system component comprises metal oxides and metal oxidesused in combination with promoters in contact with a metal oxidesupported.

According to one embodiment the catalyst system comprises catalysts (a)and (b). According to a separate embodiment, catalyst system comprises acombination of catalyst (a), (b) and (c). The catalyst are typically incontact with (preferably impregnated on) a metal oxide support having athree-dimensional structure.

The various mixed metal oxides of the present invention, as noted above,may be prepared in the following manner.

In a first step, a slurry or solution may be formed by admixing metalcompounds, preferably at least one of which contains oxygen, and atleast one solvent in appropriate amounts to form the slurry or solution.Preferably, a solution is formed at this stage of the catalystpreparation. Generally, the metal compounds contain the elementsrequired for the particular catalyst, as previously defined.

Suitable solvents include water, alcohols including, but not limited to,methanol, ethanol, propanol, and diols, etc., as well as other polarsolvents known in the art. Generally, water is preferred. The water isany water suitable for use in chemical syntheses including, withoutlimitation, distilled water and de-ionized water. The amount of waterpresent is preferably an amount sufficient to keep the elementssubstantially in solution long enough to avoid or minimize compositionaland/or phase segregation during the preparation steps. Accordingly, theamount of water will vary according to the amounts and solubilities ofthe materials combined. However, as stated above, the amount of water ispreferably sufficient to ensure an aqueous solution is formed at thetime of mixing.

For example, when a mixed metal oxide of the formulaMo_(a)V_(b)Te_(c)Nb_(d)O_(e) is to be prepared, an aqueous solution oftelluric acid, an aqueous solution of niobium oxalate and a solution orslurry of ammonium paramolybdate may be sequentially added to an aqueoussolution containing a predetermined amount of ammonium metavanadate, sothat the atomic ratio of the respective metal elements would be in theprescribed proportions.

Once the aqueous slurry or solution (preferably a solution) is formed,the water is removed by any suitable method, known in the art, to form acatalyst precursor. Such methods include, without limitation, vacuumdrying, freeze drying, spray drying, rotary evaporation and air drying.Vacuum drying is generally performed at pressures ranging from 10 mmHgto 500 mmHg. Freeze drying typically entails freezing the slurry orsolution, using, for instance, liquid nitrogen, and drying the frozenslurry or solution under vacuum. Spray drying is generally performedunder an inert atmosphere such as nitrogen or argon, with an inlettemperature ranging from 125° C. to 200° C. and an outlet temperatureranging from 75° C. to 150° C. Rotary evaporation is generally performedat a bath temperature of from 25° C. to 90° C. and at a pressure of from10 mmHg to 760 mmHg, preferably at a bath temperature of from 40° to 90°C. and at a pressure of from 10 mmHg to 350 mmHg, more preferably at abath temperature of from 40° C. to 60° C. and at a pressure of from 10mmHg to 40 mmHg. Air drying may be effected at temperatures ranging from25° C. to 90° C. Rotary evaporation or air drying are generallyemployed.

Once obtained, the catalyst precursor is calcined. The calcination isusually conducted in an oxidizing atmosphere, but it is also possible toconduct the calcination in a non-oxidizing atmosphere, e.g., in an inertatmosphere or in vacuo. The inert atmosphere may be any material whichis substantially inert, i.e., does not react or interact with, thecatalyst precursor. Suitable examples include, without limitation,nitrogen, argon, xenon, helium or mixtures thereof. Preferably, theinert atmosphere is argon or nitrogen. The inert atmosphere may flowover the surface of the catalyst precursor or may not flow thereover (astatic environment). When the inert atmosphere does flow over thesurface of the catalyst precursor, the flow rate can vary over a widerange, e.g., at a space velocity of from 1 to 500 hr⁻¹.

The calcination is usually performed at a temperature of from 350° C. to1000° C., including from 400° C. to 900° C., and including from 500° C.to 800° C. The calcination is performed for an amount of time suitableto form the aforementioned catalyst. Typically, the calcination isperformed for from 0.5 to 30 hours, preferably from 1 to 25 hours, morepreferably for from 1 to 15 hours, to obtain the desired mixed metaloxide.

In one mode of operation, the catalyst precursor is calcined in twostages. In the first stage, the catalyst precursor is calcined in anoxidizing atmosphere (e.g., air) at a temperature of from 200° C. to400° C., including from 275° C. to 325° C. for from 15 minutes to 8hours, including from 1 to 3 hours. In the second stage, the materialfrom the first stage is calcined in a non-oxidizing environment (e.g.,an inert atmosphere) at a temperature of from 500° C. to 900° C.,including from 550° C. to 800° C., for from 15 minutes to 8 hours,including from 1 to 3 hours.

Optionally, a reducing gas, such as, for example, ammonia or hydrogen,is added during the second stage calcination.

In a separate mode of operation, the catalyst precursor in the firststage is placed in the desired oxidizing atmosphere at room temperatureand then raised to the first stage calcination temperature and heldthere for the desired first stage calcination time. The atmosphere isthen replaced with the desired non-oxidizing atmosphere for the secondstage calcination, the temperature is raised to the desired second stagecalcination temperature and held there for the desired second stagecalcination time.

Although any type of heating mechanism, e.g., a furnace, may be utilizedduring the calcination, it is preferred to conduct the calcination undera flow of the designated gaseous environment. Therefore, it isadvantageous to conduct the calcination in a bed with continuous flow ofthe desired gages) through the bed of solid catalyst precursorparticles.

With calcination, a mixed metal oxide catalyst is formed having astoichiometric or non-stoichiometric amounts of the respective elements.

The invention provides also process for preparing metal oxide and mixedmetal oxide catalysts that convert alkanes to their correspondingalkenes and oxygenates at short contact times comprising the steps of;

mixing salts of metals selected from the group consisting of Mo, Te, V,Ta and Nb at temperatures above the melting point of the highest meltingsalt to form a miscible molten salt; and

calcining the mixture of salts in the presence of oxygen to provide amixed metal oxide catalyst, optionally using a metal halide salt or ametal oxyhalide salt as solvent.

The starting materials for the above mixed metal oxide are not limitedto those described above. A wide range of materials including, forexample, oxides, nitrates, halides or oxyhalides, alkoxides,acetylacetonates and organometallic compounds may be used. For example,ammonium heptamolybdate may be utilized for the source of molybdenum inthe catalyst. However, compounds such as MoO₃, MoO₂, MoCl₅, MoOCl₄,Mo(OC₂H₅)₅, molybdenum acetylacetonate, phosphomolybdic acid andsilicomolybdic acid may also be utilized instead of ammoniumheptamolybdate. Similarly, ammonium metavanadate may be utilized for thesource of vanadium in the catalyst. However, compounds such as V₂O₅,V₂O₃, VOCl₃, VCl₄, VO(OC₂H₅)₃, vanadium acetylacetonate and vanadylacetylacetonate may also be utilized instead of ammonium metavanadate.The tellurium source may include telluric acid, TeCl₄, Te(OC₂H₅)₅,Te(OCH(CH₃)₂)₄ and TeO₂. The niobium source may include ammonium niobiumoxalate, Nb₂O₅, NbCl₅, niobic acid or Nb(OC₂H₅)₅ as well as the moreconventional niobium oxalate.

Use of low-melting salts opens up a new approach to preparing mixedmetal oxide catalysts. The advantages over current aqueous suspensionmethods include higher incorporation of sparsely soluble metal salts,better control of metal ratios, and more homogeneous catalyst systems.One unique approach is to use low-melting halides of the desired MMOmetals to prepare salt solutions. Variations of this approach arediscussed below in more detail.

Halide salts of the desired metals are combined by mixing attemperatures above the melting point of the highest melting salt. Themolten salts should be miscible with each other forming a stable,homogeneous solution of molten salt.

One advantage of the method is that it eliminates the solubility limitsinherent in aqueous slurry systems. By using molten salts, we canincorporate much higher levels of such metals as niobium, vanadium, andpalladium, the salts of which have relatively low solubilities inaqueous media. Examples of metal salts and their melting points aregiven in Table 4. These salts are readily available, relativelyinexpensive, and have reasonably low melting points.

According to one embodiment, certain metal oxyhalides are useful assolvents in preparing metal oxides using the method. Vanadium halidessuch as vanadium tetrachloride, VCl₄ and vanadyl trichloride (VOCl₃),which are liquids at room temperature and are ideal solvents for thechloride salts of the other metals because of their polarity and lowboiling points (BP(VCl₄)=148° C., BP(VOCl₃)=127° C.). Metal halides aredissolved in one of these solvents in the desired mole ratios, and thenexcess vanadium is removed via evaporation under reduced pressure andinert atmosphere. The catalyst cake is then calcined under O₂/Argon toliberate oxides of chlorine, generating the mixed metal oxide catalyst.Alternatively, the catalyst cake can be calcined under wet Argon togenerate the mixed metal oxide (MMO) catalyst and HCl. In addition,mixed metal halides (MMH) are also converted to MMO, discussed in moredetail below.

According to a separate embodiment, it is advantageous to introduceoxygen earlier in the synthesis. This is achieved by mixing metal oxidesinto either the molten salt solution or the VCl₄/VOCl₃ solution. Thismethod reduces the amount of chlorine that must be removed duringcalcination and generates mixed oxychloride precursors that already havesome of the desired characteristics of the final catalyst. Onepreparation is to dissolve oxides of niobium, tellurium, and molybdenumin VCl₄/VOCl₃. The resulting precursor will already have high oxygencontent.

According to a separate embodiment, mixed metal halides (MMH) are alsoconverted to MMO. Three methods for converting mixed metal halides (MMH)and mixed metal oxyhalides (MMOH) to mixed metal oxides (MMO) aredescribed:

(A) MMH precursors are calcined under wet (1%) argon at elevatedtemperatures (600° C.). The off-gas is scrubbed with caustic to trap theproduct HCl.

(B) MMH precursors are calcined under argon with low O₂ concentration.The low O₂ concentration moderates the reaction. The oxychloride gasesis scrubbed with caustic.

(C) MMH precursors are chemically converted to the metal alkoxides undermild conditions, followed by calcination under O₂/Argon to generate theMMO catalyst. By using the alkoxide intermediate, the crystallinestructure of the final catalyst can be altered.

The MMO prepared from the molten salt method can be prepared on supportmaterials including metal oxide supports. One advantage of using moltensalt or salt solutions in VCl₄/VOCl₃ is that it is comparatively easy toimpregnate support material, such as alumina, zirconia, silica, ortitanium oxide, and allows the use of either the pearl technique orsequential loading. The relatively high metal concentrations in solutionenables one to increase the metal loading on the support material,providing an ideal catalyst for millisecond contact time reactions.

Alternatively, another approach to preparing supported MMO catalyst isaddition of finely-divided support material such as aluminum oxide intothe salt solution (molten salt or VCl₄/VOCl₃ solution) to create asuspension/slurry. After concentration and calcination, the finalcatalyst prepared is a supported MMO catalyst with significantly highersurface area.

A mixed metal oxide, thus obtained, exhibits excellent catalyticactivities by itself. However, the mixed metal oxide can be converted toa catalyst having higher activities by grinding.

There is no particular restriction as to the grinding method, andconventional methods may be employed. As a dry grinding method, a methodof using a gas stream grinder may, for example, be mentioned whereincoarse particles are permitted to collide with one another in a highspeed gas stream for grinding. The grinding may be conducted not onlymechanically but also by using a mortar or the like in the case of asmall scale operation.

As a wet grinding method wherein grinding is conducted in a wet state byadding water or an organic solvent to the above mixed metal oxide, aconventional method of using a rotary cylinder-type medium mill or amedium-stirring type mill, may be mentioned. The rotary cylinder-typemedium mill is a wet mill of the type wherein a container for the objectto be ground is rotated, and it includes, for example, a ball mill and arod mill. The medium-stirring type mill is a wet mill of the typewherein the object to be ground, contained in a container is stirred bya stirring apparatus, and it includes, for example, a rotary screw typemill, and a rotary disc type mill.

The conditions for grinding may suitably be set to meet the nature ofthe above-mentioned mixed metal oxide; the viscosity, the concentration,etc. of the solvent used in the case of wet grinding; or the optimumconditions of the grinding apparatus. However, it is preferred thatgrinding is conducted until the average particle size of the groundcatalyst precursor would usually be at most 20 μm, more preferably atmost 5 μm. Improvement in the catalytic performance may be brought aboutby such grinding.

Further, in some cases, it is possible to further improve the catalyticactivities by further adding a solvent to the ground catalyst precursorto form a solution or slurry, followed by drying again. There is noparticular restriction as to the concentration of the solution orslurry, and it is usual to adjust the solution or slurry so that thetotal amount of the starting material compounds for the ground catalystprecursor is from 10 to 60 wt %. Then, this solution or slurry is driedby a method such as spray drying, freeze drying, evaporation to drynessor vacuum drying. Further, similar drying may be conducted also in thecase where wet grinding is conducted.

The oxide obtained by the above-mentioned method may be used as a finalcatalyst, but it may further be subjected to heat treatment usually at atemperature of from 200° to 800° C. for from 0.1 to 10 hours.

The mixed metal oxide thus obtained is typically used by itself as asolid catalyst, but may be formed into a catalyst together with asuitable carrier such as silica, alumina, titania, aluminosilicate,diatomaceous earth or zirconia. Further, it may be molded into asuitable shape and particle size depending upon the scale or system ofthe reactor.

Alternatively, the metal components of the presently contemplatedcatalyst may be supported on materials such as alumina, silica,silica-alumina, zirconia, titania, etc. by conventional incipientwetness techniques. In one typical method, solutions containing themetals are contacted with the dry support such that the support iswetted; then, the resultant wetted material is dried, for example, at atemperature from room temperature to 200° C. followed by calcination asdescribed above. In another method, metal solutions are contacted withthe support, typically in volume ratios of greater than 3:1 (metalsolution support), and the solution agitated such that the metal ionsare ion-exchanged onto the support. The metal containing support is thendried and calcined as detailed above.

When using a catalyst system including two or more catalysts, thecatalyst may be in the form of a physical blend of the severalcatalysts. Preferably, the concentration of the catalysts may be variedso that the first catalyst component will have a tendency to beconcentrated at the reactor inlet while subsequent catalysts will have atendency to be concentrated in sequential zones extending to the reactoroutlet. Most preferably, the catalysts will form a layered bed (alsoreferred to a mixed bed catalyst), with the first catalyst componentforming the layer closest to the reactor inlet and the subsequentcatalysts forming sequential layers to the reactor outlet. The layersabut one another or may be separated from one another by a layer ofinert material or a void space.

The short contact time reactor is of a type suitable for the use of afixed catalyst bed in contact with a gaseous stream of reactants. Forinstance, a shell and tube type of reactor may be utilized, wherein oneor more tubes are packed with catalyst(s) so as to allow a reactant gasstream to be passed in one end of the tube(s) and a product stream to bewithdrawn from the other end of the tube(s). The tube(s) being disposedin a shell so that a heat transfer medium may be circulated about thetube(s).

In the case of the utilization of a single catalyst, hybrid catalyst,catalyst system or hybrid catalyst system, the gas stream comprising thealkane, molecular oxygen and any additional reactant feeds including butnot limited to alkenes, oxygen, air, hydrogen, carbon monoxide, carbondioxide, formaldehyde and alcohols, steam and any diluents includingnitrogen, argon may all be fed into the front end(s) of the tube(s)together. Alternatively, the alkane and the molecular oxygen-containinggas may be fed into the front end(s) of the tube(s) while the additionalreactants, steam and diluents may be fed (also referred to as staging)into the tube(s) at a predetermined downstream location (typicallychosen so as to have a certain minimum concentration of product alkenepresent in the gas stream passing through the tube(s), e.g., 3%,preferably 5%, most preferably 7%).

In the case of the utilization of catalyst systems including two or morecatalysts, e.g., a first catalyst component and a second catalystcomponent as described above, once again the gas stream comprising thealkane, the oxygen-containing gas and any additional reactant feedsincluding but not limited to alkenes, oxygen, air, hydrogen, carbonmonoxide, carbon dioxide, formaldehyde and alcohols, steam and anydiluents including nitrogen, argon are fed to the front end(s) of thetube(s) together. Alternatively, and preferably, the alkane and themolecular oxygen-containing gas are staged into the front end(s) of thetube(s) while any additional reactant feeds, steam and diluents arestaged into the tube(s) at a predetermined downstream location(typically chosen so at have a certain minimum concentration of desiredproduct present in the gas stream passing through the tube(s),as setforth above; or in the case of the utilization of layered beds ofcatalyst, as described above, intermediate two layered catalyst beds).

In addition to molecular oxygen, carbon dioxide is also employed as amuch milder oxidizing agent in the multi-stage method of the invention.One advantage of the invention is that carbon dioxide is generated bysacrificing a small portion of the alkane in the initial step of steamcracking in addition to steam using conventional steam crackingcatalysts well known in the art. In addition to providing a milderoxidant the exothermic nature of converting alkane to alkene isminimized which in turn minimizes over oxidation products, including butnot limited to CO, alkane fragments and alkene fragments andcombinations thereof. A second advantage is that unlike molecularoxygen, carbon dioxide will not induce gas-phase radical reactions. Suchoxidative coupling reactions will be controlled by heterogeneouscatalysts. As a consequence and according to an exemplary embodiment,methane can be oxidatively coupled to provide ethylene without overoxidation as well methane and ethane cane be combined and catalyticallyconverted to propylene. Suitable catalysts include but are not limitedto PbO/MgO, lanthanide oxides, mixtures of lanthanide oxides, CaO/CeO₂,metal oxides, combinations of Group 1-3 oxides and metal oxides such asCaO/MnO₂, CaO/Cr₂O₃, CaO/ZnO, combinations of metal oxides,multi-component metal oxide catalysts, supported metal oxides asdescribed earlier such as SiO₂/Cr₂O₃, certain non metal oxides, certainnon-oxide metals and combinations thereof.

According to a separate embodiment, alkanes, including but not limitedto for example ethane, propane, isobutane, and butane are oxidized totheir corresponding alkenes using carbon dioxide and steam in a steamcracking process by partially sacrificing some initial alkane togenerate carbon dioxide as an oxidizing agent and combining the oxidantwith the remaining corresponding alkane. Another advantage of theinvention as described earlier is that unwanted reactions that lead tocoking at higher temperatures are minimized in addition to completeoxidation of molecular hydrogen, allowing the oxidation to occur atlower temperatures, further minimizing over oxidation of the alkane.Suitable catalysts in addition to those described above include but arenot limited to for example metal oxide catalysts, mixed metal oxidecatalysts, multi-component metal oxide catalysts, including supportedmetal oxides as described earlier such as K—Cr—Mn/SiO₂, SiO₂/Cr₂O₃ andFe/Mn silicate, and combinations thereof. Another advantage of carbondioxide as an oxidant is that their redox properties dominates thecatalytic process including unwanted radical processes. Carbon dioxideproduces active oxygen species that act as oxidants, carbon dioxidereoxidizes reduced oxides forming a continuous redox cycle and carbondioxide oxidizes carbon, reducing coking. Typical reaction conditionsfor the oxidation of alkanes to corresponding alkenes which are utilizedin the practice of the present invention include: steam crackingreaction temperatures which can vary from 200° C. to 700° C.Conventional steam cracking reactors and catalysts are well known in theart and are described in the journal Energy & Fuels, 18 1126-1139, 2004.

Typical reaction conditions for the oxidation of alkenes including butnot limited to for example ethylene, propylene, butylene or isobutyleneto acrylic acid or methacrylic acid including respective esters thereofwhich are utilized in the practice of the present invention include:reaction temperatures which can vary from 300° C. to 1000° C., but areusually in the range of flame temperatures (from 500° C. to 1000° C.);the average contact time with the catalyst (i.e. the reactor residencetime) is not more than 100 milliseconds, including not more than 80milliseconds, and including not more than 50 milliseconds; the pressurein the reaction zone usually ranges from 0 to 75 psig, including no morethan 50 psig.

The invention provides a multi-stage process for preparing unsaturatedcarboxylic acids from corresponding alkanes, the process comprising thesteps of:

-   -   (a) combining 5-30% by weight of a gaseous alkane, and a        stoichiometric amount of molecular oxygen, fully oxidizing the        alkane to carbon dioxide and water vapor in the form of steam;    -   (b) combining the steam and the remaining amount of alkane with        the steam and carbon dioxide and directing it to contact one or        more stem cracking catalysts; and    -   (c) converting the corresponding alkene generated from (b) and        molecular oxygen to a short contact time reactor, the reactor        including a mixed catalyst bed comprising (1) a first catalyst        layer comprising (i) at least one metal selected from the group        consisting of Ag, Au, Ir, Ni, Pd, Pt, Rh, Ru, alloys thereof and        combinations thereof; and (ii) at least one modifier selected        from the group of metal oxides including the metals Bi, In, Mg,        P, Sb, Zr, Group 1-3 metals, lanthanide metals and combinations        thereof, in combination with or without (iii) at least one metal        oxide including the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Nb, Ta,        V, Zn, binary combinations thereof, ternary combinations thereof        and higher combinations thereof, wherein the catalysts of the        first layer are impregnated on a metal oxide support; and (2) a        second catalyst layer comprising at least one metal oxide        including the metals Mo, Fe, P, V and combinations thereof, the        mixed bed catalyst cumulatively effective at converting the        gaseous alkane to its corresponding gaseous unsaturated        carboxylic acid;

wherein the second catalyst layer is separated at a distance downstreamfrom the first catalyst layer and the reactor is operated at atemperature of from 500° C. to 1000° C., with a reactor residence timeof no greater than 100 milliseconds; and wherein the one or morecracking catalysts is separated at a distance upstream from the shortcontact time reactor.

As a separate embodiment, the present invention provides a multi-stageprocess for preparing unsaturated carboxylic acids from correspondingalkanes, the process comprising the steps of

-   -   (a) combining 5-30% by weight of a gaseous alkane, and a        stoichiometric amount of molecular oxygen, fully oxidizing the        alkane to carbon dioxide and water vapor in the form of steam;    -   (b) combining the steam and the remaining amount of alkane with        the steam and carbon dioxide and directing it to contact one or        more stem cracking catalysts; and    -   (c) converting the corresponding alkene generated from (b) and        molecular oxygen to a short contact time reactor, the reactor        including a mixed catalyst bed comprising (1) a first catalyst        layer comprising (i) at least one metal selected from the group        consisting of Ag, Au, Ir, Ni, Pd, Pt, Rh, Ru, alloys thereof and        combinations thereof, and (ii) at least one modifier selected        from the group of metal oxides including the metals Bi, In, Mg,        P, Sb, Zr, Group 1-3 metals, lanthanide metals and combinations        thereof, in combination with or without (iii) at least one metal        oxide including the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Nb, Ta,        V, Zn, binary combinations thereof, ternary combinations thereof        and higher combinations thereof, wherein the catalysts of the        first layer are impregnated on a metal oxide support; and (2) a        second catalyst layer comprising at least one metal oxide        including the metals Mo, Fe, P, V and combinations thereof, the        mixed bed catalyst cumulatively effective at converting the        gaseous alkane to its corresponding gaseous unsaturated        carboxylic acid;

wherein the one or more cracking catalysts is separated at a distanceupstream from the short contact time reactor;

the first catalyst zone being disposed upstream of the second catalystzone relative to the direction of flow of the gaseous stream through thereactor;

the first catalyst zone being operated at a temperature of from 500° C.to 1000° C., with a first reaction zone residence time of no greaterthan 100 milliseconds;

the second catalyst zone being operated at a temperature of from 300° C.to 400° C., with a second reaction zone residence time of no greaterthan 100 milliseconds;

wherein the gaseous stream of the alkane is passed through the reactorin a single pass or wherein any unreacted alkane is recycled back intothe gaseous stream of alkane entering the reactor and wherein anysaturated carboxylic acid is recycled back into the second catalyst zoneto increase the overall yield of unsaturated carboxylic acid.

It is useful to pass a gaseous stream comprising propane or isobutaneand molecular oxygen to the reactor. In addition, the feed may containan additional reactant, adjuvant such as steam or a diluent such as aninert gas, e.g., nitrogen, argon or a milder oxidant including carbondioxide.

In a separate embodiment, the gaseous stream of the alkane or alkene ispassed through its respective SCR or SCTR in a single pass or whereinany unreacted alkane or alkene is recycled back into the gaseous streamof alkene entering its respective SCTR and any saturated carboxylic acidis recycled back into the second catalyst zone to increase the overallyield of unsaturated carboxylic acid.

The invention also provides a multi-stage process comprising the stepsof: (a) cumulatively converting an alkane to its corresponding alkeneusing one or more steam cracking catalysts, (b) catalytically convertingthe corresponding alkene to further corresponding oxygenated productsselected from unsaturated carboxylic acid, and higher analogueunsaturated carboxylic acid in a short contact time reactor using thecatalyst systems of the invention; and (c) adding the resulting productor products to the front end of a second fixed bed oxidation reactorwith the product(s) from the first reactor acting as feed to the secondreactor. For example, propane is first steam cracked and catalyticallyconverted to propylene and the propylene is further catalyticallyconverted to corresponding oxygenates using a catalyst system in a shortcontact time reactor. The propylene is fed to the second oxidationreactor that converts its to acrylic acid. According to one embodimentthis includes feeding any unreacted alkane from the first reactor andany unreacted alkene from the the second reactor to recycle therespective alkane and alkene. For example, any unreacted propane isrecycled to the first steam cracking reactor or SCR or optionally addedas a feed to the second oxidation reactor. The second oxidation reactorcomprises any conventional industrial scale oxidation reactor used forconverting alkenes to unsaturated carboxylic acids at longer residencetimes (seconds). Alternatively, the second oxidation reactor comprises asecond SCTR operating at millisecond residence times.

Any source of molecular oxygen may be employed in this process, e.g.,oxygen, oxygen-enriched gases or air. Air may be the most economicalsource of oxygen, especially in the absence of any recycle.

Alternatively, the metal oxide catalyst components or second catalystlayer may comprise:

-   -   (A) a mixed metal oxide catalyst having the empirical formula

Mo_(a)V_(b)M_(c)N_(d)O_(e)

-   -   wherein    -   M is selected from the group consisting of Te and Sb,    -   N is at least one element selected from the group consisting of        Nb, Ta, W, Ti, Al, Zr, Cr, Mn, B, In, As, Ge, Sn, Li, Na, K, Rb,        Cs, Fr, Be, Mg, Ca, Sr, Ba, Hf and P,    -   a, b, c, d and e represent relative atomic amounts of the        elements, and    -   when a=1, b=0.01 to 1.0, c=0.01 to 1.0, d=0.01 to 1.0 and e        depends on the oxidation state of the elements other than        oxygen. At flame temperatures, certain metal components,        including Mo and Te, of the mixed metal oxide catalyst        volatilize leaving different mixed metal oxide catalysts,        intermetallic catalysts and hybrid catalysts thereof.    -   (B) a catalyst comprising a mixed metal oxide having the        empirical formula

Mo_(a)Sb_(b)O_(c)

-   -   wherein    -   a, b and c represent relative atomic amounts of the elements,        and    -   when a=1, b=0.01 to 1.0 and c depends on the oxidation state of        the elements other than oxygen. At flame temperatures, certain        metal components of the mixed metal oxide catalyst volatilize        leaving different mixed metal oxide catalysts, intermetallic        catalysts and hybrid catalysts thereof.    -   (C) a catalyst comprising a mixed metal oxide having the        empirical formula

Mo_(a)Sb_(b)Bi_(c)O_(d)

-   -   wherein    -   a, b, c and d represent relative atomic amounts of the elements,        and when a=1, b=0.01 to 1.0, c=0.01 to 1.0 and d depends on the        oxidation state of the elements other than oxygen. At flame        temperatures, certain metal components of the mixed metal oxide        catalyst volatilize leaving different mixed metal oxide        catalysts, intermetallic catalysts and hybrid catalysts thereof.

Alternatively, the catalyst may comprise combinations of catalysts (A),(B) and (C).

Yet other alternative oxidation catalysts may comprise:

-   -   (a) a supported catalyst comprising at least one element        selected from the group consisting of Groups 5B, 6B, 7B, and 8        of the periodic table of the elements promoted with at least one        element selected from Group 1B of the periodic table of the        elements plus bismuth oxide acetate; or    -   (b) a catalyst comprising ruthenium; or    -   (c) a catalyst comprising Pd and Bi on a support; or    -   (d) a supported catalyst comprising Pd and at least one element        selected from the group consisting of elements of Groups 3A, 4A,        5A and 6B of the periodic table of the elements and at least one        element selected from the group consisting of elements of Groups        3B and 4B of the periodic table of the elements; or    -   (e) a supported catalyst comprising Pd and at least one element        of Group 1B of the periodic table of the elements; or    -   (f) a supported catalyst comprising Pd and Pb; or    -   (g) a supported catalyst comprising Pd and at least one element        selected from the group consisting of Ba, Au, La, Nb, Ce, Zn,        Pb, Ca, Sb, K, Cd, V and Te; or    -   (h) combinations thereof.

Another alternative catalyst comprises a phosphate catalyst containingMo, V, Nb and/or Ta. (See Japanese Laid-Open Patent ApplicationPublication No. 06-199731 A2.). Yet another alternative catalystcomprises any of the well-known molybdenum, bismuth, iron-based mixedmetal oxides such as those disclosed in U.S. Pat. Nos. 3,825,600;3,649,930 and 4,339,355.

The invention also provides a multi-stage process for the production ofesters of unsaturated carboxylic acids, the process comprising the stepsof:

-   -   (a) combining 5-30% by weight of a gaseous alkane, and a        stoichiometric amount of molecular oxygen, fully oxidizing the        alkane to carbon dioxide and water vapor in the form of steam;    -   (b) combining the steam and the remaining amount of alkane with        the steam and carbon dioxide and directing it to contact one or        more stem cracking catalysts; and    -   (c) converting the corresponding alkene generated from (b) and        molecular oxygen to a short contact time reactor, the reactor        including a mixed catalyst bed comprising (1) a first catalyst        layer comprising (i) at least one metal selected from the group        consisting of Ag, Au, Ir, Ni, Pd, Pt, Rh, Ru, alloys thereof and        combinations thereof; and (ii) at least one modifier selected        from the group of metal oxides including the metals Bi, In, Mg,        P, Sb, Zr, Group 1-3 metals, lanthanide metals and combinations        thereof, in combination with or without (iii) at least one metal        oxide including the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Nb, Ta,        V, Zn, binary combinations thereof, ternary combinations thereof        and higher combinations thereof, wherein the catalysts of the        first layer are impregnated on a metal oxide support; and (2) a        second catalyst layer comprising at least one metal oxide        including the metals Mo, Fe, P, V and combinations thereof, the        mixed bed catalyst cumulatively effective at converting the        gaseous alkane to its corresponding gaseous unsaturated        carboxylic acid;

wherein the one or more cracking catalysts is separated at a distanceupstream from the short contact time reactor;

wherein the second catalyst layer is separated at a distance downstreamfrom the first catalyst layer and the reactor is operated at atemperature of from 500° C. to 1000° C., with a reactor residence timeof no greater than 100 milliseconds.

According to one embodiment, an additional catalyst layer is includedbetween the first and second layers comprising at least one metal oxideincluding the metals Mo, Fe, P, V and combinations thereof, the catalystadditional layer cumulatively effective at converting the gaseoussaturated carboxylic acid to its corresponding gaseous unsaturatedcarboxylic acid before it is catalytically converted to itscorresponding ester in the presence of an alcohol.

The invention also provides a multi-stage process for cumativelyconverting alkanes to their corresponding esters of unsaturatedcarboxylic acids, the reactor containing one or more oxidation catalystscumulatively effective for converting the alkane to an ester of itscorresponding unsaturated carboxylic acid with the alcohol; the one ormore oxidation catalysts comprising a first catalyst system effectivefor converting the alkane to its corresponding unsaturated carboxylicacid and a second catalyst effective for converting the ethylenicallyunsaturated alcohol, in the presence of the alcohol, to an ester of itscorresponding ethylenically unsaturated carboxylic acid with thealcohol;

the first catalyst being disposed in a first reaction zone;

the second catalyst being disposed in a second reaction zone;

the first reaction zone being disposed upstream of the second reactionzone relative to the direction of flow of the first gaseous streamthrough the reactor;

the second gaseous stream being fed to the reactor intermediate thefirst reaction zone and the second reaction zone;

the first reaction zone being operated at a temperature of from 500° C.to 1000° C., with a first reaction zone residence time of no greaterthan 100 milliseconds;

the second reaction zone being operated at a temperature of from 300° C.to 400° C., with a second reaction zone residence time of no greaterthan 100 milliseconds.

According to yet another embodiment, provides a multi-stage process forcatalytically and cumulatively converting alkanes to their correspondinghigher unsaturated carboxylic acids and then catalytically convertingthem to their corresponding esters in the presence of specific alcohols.

In preparing esters of ethylenically unsaturated carboxylic acids andhigher analogues thereof using the multi-staged catalyst systems of theinvention, it is useful to pass a first gaseous stream comprisingpropane or isobutane and molecular oxygen to the SCR to generate carbondioxide and oxidize the remaining alkanes to corresponding alkenespropylene and isobutylene; to pass the corresponding alkenes to a SCTRwith one or more oxidation catalysts to cumulatively convert the alkenesto corresponding unsaturated carboxylic acids and to separately pass asecond gaseous stream comprising the alcohol to the reactor. Inaddition, the feed may contain an additional reactant, adjuvant such assteam or a diluent such as an inert gas, e.g., nitrogen, argon oradditional oxidants including carbon dioxide. Any additional reactantfeeds include but are not limited to alkenes, oxygen, air, hydrogen,carbon monoxide, carbon dioxide, and formaldehyde.

It is useful to pass, a first gaseous stream comprising propane orisobutane and molecular oxygen to the SCR then the corresponding alkenegaseous stream to the SCTR; and to separately pass a second gaseousstream comprising the alcohol and any additional feed to the SCTR. Inaddition, the feed may contain an adjuvant such as steam or a diluentsuch as an inert gas, e.g., nitrogen, argon or carbon dioxide.

Any source of molecular oxygen or other milder oxidants including carbondioxide may be employed in this process, e.g., oxygen, oxygen-enrichedgases or air. Air may be the most economical source of oxygen,especially in the absence of any recycle.

An alternative first catalyst may comprise a mixed metal oxide havingthe empirical formula

Mo_(a)V_(b)M_(c)N_(d)Q_(e)X_(f)O_(g)

wherein

-   M is an element selected from the group consisting of Te and Sb,-   N is at least one element selected from the group consisting of Nb,    Ta, W, Ti, Al, Zr, Cr, Mn, B, In, As, Ge, Sn, Li, Na, K, Rb, Cs, Fr,    Be, Mg, Ca, Sr, Ba, Hf and P,-   Q is at least one element selected from Group 8 of the periodic    table of the elements,-   X is at least one element selected from the group consisting of Pb    and Bi, a, b, c, d, e, f and g represent relative atomic amounts of    the elements, and

when a=1, b=0.01 to 1.0, c=0.01 to 1.0, d=0.01 to 1.0, e=0.001 to 0.1,f=0.001 to 0.1 and g depends on the oxidation state of the elementsother than oxygen. At flame temperatures, certain metal components,including Mo and Te, of the mixed metal oxide catalyst volatilizeleaving different mixed metal oxide catalysts, intermetallic catalystsand hybrid catalysts thereof.

Another alternative first catalyst comprises a phosphate catalystcontaining Mo, V, Nb and/or Ta. (See Japanese Laid-Open PatentApplication Publication No.06-199731 A2.).

Yet another alternative first catalyst comprises a mixed metal oxidehaving the formula P_(a)Mo_(b)V_(c)Bi_(d)X_(e)Y_(f)Z_(g)O_(h), wherein Xis As, Sb, Si, B, Ge or Te; Y is K, Cs, Rb, or Tl; Z is Cr, Mn, Fe, Co,Ni, Cu, Al, Ga, In, Sn, Zn, Ce, Y or W; a, b, c, d, e, f, g and h arethe relative atomic amounts of the elements; and, when b=12, 0<a≦3,c=0-3, 0<d≦3, 0<e≦3, f=0-3, g=0-3, and h depends on the oxidation stateof the other elements. (See Japanese Laid-Open Patent applicationPublication No. 09-020700 A2.).

Other alternative mixed metal oxide catalysts are usefully employed andhave been described earlier in the specification.

The second catalyst is useful for catalyzing conversion of theethylenically unsaturated carboxylic acid to its corresponding ester.

The second catalyst comprises a superacid. A superacid, according to thedefinition of Gillespie, is an acid that is stronger than 100% sulfuricacid, i.e. it has a Hammett acidity value H₀<−12. Representativesuperacids include, but are not limited to: zeolite supportedTiO₂/(SO₄)₂, (SO₄)₂/ZrO₂—TiO₂, (SO₄)₂/ZrO₂—Dy₂O₃, (SO₄)₂/TiO₂,(SO₄)₂/ZrO₂—NiO, SO₄/ZrO₂, SO₄/ZrO_(2.)Al₂O₃, (SO₄)₂/Fe₂O₃, (SO₄)₂/ZrO₂,C₄F₉SO₃H—SbF₅, CF₃SO₃H—SbF₅, Pt/sulfated zirconium oxide, HSO₃F—SO₂ClF,SbF₅—HSO₃F—SO₂ClF, MF₅/AlF₃ (M=Ta, Nb, Sb), B(OSO₂CF₃)₃,B(OSO₂CF₃)₃—CF₃SO₃H, SbF₅—SiO₂—Al₂O₃, SbF₅—TiO₂—SiO₂ and SbF₅—TiO₂.Preferably, solid superacids are utilized, e.g., sulfated oxides,supported Lewis acids and supported liquid superacids. Only a smallnumber of oxides produce superacid sites on sulfation, including ZrO₂,TiO₂, HfO₂, Fe₂O₃ and SnO₂. The acid sites are generated by treating anamorphous oxyhydrate of these elements with H₂SO₄ or (NH₄)₂SO₄ andcalcining the products at temperatures of 500° C.-650° C. During thecalcination, the oxides are transformed into a crystalline tetragonalphase, which is covered by a small number of sulfate groups. H₂MoO₄ orH₂WO₄ may also be used to activate the oxide.

Yet another alternative catalyst comprises any of the well-knownmolybdenum, bismuth, iron-based mixed metal oxides such as thosedisclosed in U.S. Pat. Nos. 3,825,600; 3,649,930 and 4,339,355.

In a separate embodiment, there is provided a multi-stage process forthe production of esters of unsaturated carboxylic acids, the processcomprising: passing a first gaseous stream comprising an alkane andmolecular oxygen to a reactor; passing a second gaseous streamcomprising an alcohol to the reactor; the reactor containing one or moreoxidation catalysts cumulatively effective for the oxidation of thealkane to an ester of its corresponding unsaturated carboxylic acid withthe alcohol; the one or more oxidation catalysts comprising a firstcatalyst effective for the oxidation of the alkane to its correspondingalkene, a second catalyst effective for the oxidation of the alkene toits corresponding unsaturated aldehyde, and a third catalyst effectivefor the oxidation of the unsaturated aldehyde, in the presence of thealcohol, to an ester of its corresponding unsaturated carboxylic acidwith the alcohol; the first catalyst being disposed in a first reactionzone; the second catalyst being disposed in a second reaction zone; thethird catalyst being disposed in a third reaction zone; the firstreaction zone being disposed upstream of the second reaction zonerelative to the direction of flow of the first gaseous stream throughthe reactor; the second reaction zone being disposed upstream of thethird reaction zone relative to the direction of flow of the firstgaseous stream through the reactor; the second gaseous stream being fedto the reactor intermediate the second reaction zone and the thirdreaction zone; the first reaction zone being operated at a temperatureof from 500° C. to 900° C., with a first reaction zone residence time ofno greater than 100 milliseconds; the second reaction zone beingoperated at a temperature of from 300° C. to 400° C., with a secondreaction zone residence time of no greater than 100 milliseconds; thethird reaction zone being operated at a temperature of from 100° C. to300° C., with a third reaction zone residence time of no greater than100 milliseconds.

In this aspect of the invention, it is useful to pass a first gaseousstream comprising propane or isobutane and molecular oxygen to the SCRand the corresponding alkene gaseous stream to the SCTR; and toseparately pass a second gaseous stream comprising the alcohol to theSCTR. In addition, the feed may contain an adjuvant such as steam or adiluent such as an inert gas, e.g., nitrogen, argon or additionaloxidants including carbon dioxide.

Any source of molecular oxygen or milder oxidants including carbondioxide may be employed in this process, e.g., oxygen, oxygen-enrichedgases or air. Air may be the most economical source of oxygen,especially in the absence of any recycle.

The appropriate catalyst is selected from respective catalysts describedpreviously. Alternative catalyst components may comprise a reduciblemetal oxide promoted with a metal selected from Group 8 of the periodictable of the elements and supported on a three-dimensional supportstructure.

The support structure is three-dimensional, i.e. has dimensions alongthe x, y and z orthogonal axes of a Cartesian coordinate system, andaffords a relatively high surface area per unit volume. Though lower andhigher amounts are possible, in one embodiment, the support structureexhibits a surface area of 0.01 to 50 m²/g, preferably 0.1 to 10 m²/g.

Preferably, the support structure will have a porous structure andexhibit a pore volume percent ranging from 1 to 95%, more preferably 5to 80%, and still more preferably 10 to 50%. Thus, the support structurepermits relatively high feed velocities with insubstantial pressuredrop.

Further, the support structure is sufficiently strong so that it doesnot fracture under the weight of the catalyst, which can range up toalmost 100% of the weight of the combination of the catalyst and thesupport structure. More preferably, however, the support structure is atleast 60% of the weight of the combination. Still more preferably, it is70 to 99.99% of the weight of the combination. Even still morepreferably, the support structure is 90 to 99.9% of the weight of thecombination.

The exact physical form of the support structure is not particularlyimportant so long as it meets the above noted general criteria. Examplesof suitable physical forms include foam, honeycomb, lattice, mesh,monolith, woven fiber, non-woven fiber, gauze, perforated substrates(e.g., foil), particle compacts, fibrous mat and mixtures thereof. Forthese supports it will be appreciated that typically one or more opencells will be included in the structure. The cell size may vary asdesired, as may the cell density, cell surface area, open frontal areaand other corresponding dimensions. By way of example, one suchstructure has an open frontal area of at least 75%. The cell shape mayalso vary and may include polygonal shapes, circles, ellipses, as wellas others.

The support structure may be fabricated from a material that is inert tothe reaction environment of the catalytic reaction. Suitable materialsinclude ceramics such as silica, alumina, silica-alumina,aluminosilicate, zirconia, titania, boria, mullite, lithium aluminumsilicate, oxide-bonded silicon carbide or mixtures thereof.(Alternatively, the catalyst may be prepared so as to define the supportstructure itself, e.g., by “green” compacting or another suitabletechnique.)

The catalysts may be applied to the support structure using any suitableart-disclosed technique. For instance, the catalyst may be vapordeposited (e.g., by sputtering, plasma deposition or some other form ofvapor deposition). The catalyst may be coated thereon (e.g., by washcoating a support with a solution, slurry, suspension or dispersion ofcatalyst). The support may be coated with a catalyst powder (i.e. powdercoating). (Alternatively, where the support structure is the catalystitself, a “green” body of catalyst may be compacted to yield the desiredstructure.)

The appropriate first catalyst is selected from catalysts describedpreviously. Alternative first catalyst are also selected from catalystsdescribed previously. Alternative first catalyst may be a binary,ternary, quaternary or higher order metal oxides. The reducible metaloxide may be an oxide of a metal selected from the group consisting ofCu, Cr, V, Mn, Nb, Mo, W, Re, Ga, Ge, In, Sn, Sb, Tl, Pb, Bi, Te, As,Se, Zn, Y, Zr, Ta, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,Lu and mixtures thereof. Preferably, the reducible metal oxide isselected from the group consisting of Cu, Cr, V, Mn, Zn and mixturesthereof. The promoter is a metal from Group 8 of the periodic table ofthe elements (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt), preferably a metalselected from the group consisting of Pt, Pd, Rh, Ir, Ru and mixturesthereof. The promoter may preferably be present in an amount of from0.0001 to 10 wt % of the catalyst composition (promoter plus reduciblemetal oxide), more preferably from 0.001 to 5 wt % of the catalystcomposition, and still more preferably from 0.01 to 2 wt % of thecatalyst composition.

The appropriate second catalyst is selected from catalysts describedpreviously. Alternative second catalysts may comprise any of thewell-known molybdenum, bismuth, iron-based mixed metal oxides such asthose disclosed in U.S. Pat. Nos. 3,825,600; 3,649,930 and 4,339,355.

The appropriate third catalyst is selected from catalysts describedpreviously. The third catalyst comprises a superacid. A superacid,according to the definition of Gillespie, is an acid that is strongerthan 100% sulfuric acid, i.e. it has a Hammett acidity value H₀<−12.Representative superacids include, but are not limited to: zeolitesupported TiO₂/(SO₄)₂, (SO₄)₂/ZrO₂—TiO₂, (SO₄)₂/ZrO₂—Dy₂O₃, (SO₄)₂/TiO₂,(SO₄)₂/ZrO₂—NiO, SO₄/ZrO₂, SO₄/ZrO₂Al₂O₃, (SO₄)₂/Fe₂O₃, (SO₄)₂/ZrO₂,C₄F₉SO₃H—SbF₅, CF₃SO₃H—SbF₅, Pt/sulfated zirconium oxide, HSO₃F—SO₂ClF,SbF₅—HSO₃F—SO₂ClF, MF₅/AlF₃ (M=Ta, Nb, Sb), B(OSO₂CF₃)₃,B(OSO₂CF₃)₃—CF₃SO₃H, SbF₅—SiO₂—Al₂O₃, SbF₅—TiO₂—SiO₂ and SbF₅—TiO₂.Preferably, solid superacids are utilized, e.g., sulfated oxides,supported Lewis acids and supported liquid superacids. Only a smallnumber of oxides produce superacid sites on sulfation, including ZrO₂,TiO₂, HfO₂, Fe₂O₃ and SnO₂. The acid sites are generated by treating anamorphous oxyhydrate of these elements with H₂SO₄ or (NH₄)₂SO₄ andcalcining the products at temperatures of 500° C.-650° C. During thecalcination, the oxides are transformed into a crystalline tetragonalphase, which is covered by a small number of sulfate groups. H₂MoO₄ orH₂WO₄ may also be used to activate the oxide.

In a further separate embodiment of the invention, there is provided aprocess for the production of esters of unsaturated carboxylic acids,the process comprising: reacting an unsaturated aldehyde with an alcoholto form an acetal; passing a gaseous stream comprising the so-formedacetal and molecular oxygen to a reactor; the reactor containing atleast one catalyst effective for the oxidation of the acetal to itscorresponding ester; the reactor being operated at a temperature of from300° C. to 1000° C., with reactor residence time of no greater than 100milliseconds.

In a separate embodiment of the present invention, an alcohol is reactedwith an unsaturated aldehyde to form an acetal. Such reaction can becarried out by contacting the aldehyde with an excess of the anhydrousalcohol in the presence of a small amount of an anhydrous acid, e.g.,anhydrous HCl. Preferably, the aldehyde and the alcohol can be passedthrough a bed containing an acid catalyst, e.g., through a bed of astrongly acidic ion exchange resin, such as Amberlyst 15.

The so-formed acetal and molecular oxygen are fed to a reactorcontaining at least one catalyst effective for the oxidation of theacetal to its corresponding ester. Examples of such a catalyst includePd and Bi on alumina or V oxides.

In this aspect of the invention, any source of molecular oxygen may beemployed in this process, e.g., oxygen, oxygen-enriched gases or air.Air may be the most economical source of oxygen, especially in theabsence of any recycle.

In a separate embodiment of this aspect of the invention, theunsaturated aldehyde is formed by oxidation of an alkane to itscorresponding unsaturated aldehyde. This oxidation may be effected as avapor phase oxidation of the alkane in the presence of a catalyst suchas Pd and Bi on alumina or V oxides.

EXAMPLES Comparative Example 1 Pt Impregnated onMo_(a)V_(b)M_(c)N_(d)Q_(e)X_(f)O_(g), Wash Coated onto an Alumina Foam

An aqueous solution (200 mL) containing ammonium heptamolybdatetetrahydrate (1.0M Mo), ammonium metavanadate (0.3M V) and telluric acid(0.23M Te) formed by dissolving the corresponding salts in water at 70°C., was added to a 2000 mL rotavap flask. Then 200 mL of an aqueoussolution of ammonium niobium oxalate (0.17M Nb), oxalic acid (0.155M),palladium nitrate hydrate (0.01M Pd), and nitric acid (0.24M HNO₃) wereadded thereto. After removing the water via a rotary evaporator with awarm water bath at 50° C. and 28 mm Hg, the solid materials were furtherdried in a vacuum oven at 25° C. overnight and then calcined.(Calcination was effected by placing the solid materials in an airatmosphere and then heating them to 275° C. at 10° C./min and holdingthem under the air atmosphere at 275° C. for one hour; the atmospherewas then changed to argon and the material was heated from 275° C. to600° C. at 2° C./min and the material was held under the argonatmosphere at 600° C. for two hours.) The final catalyst had a nominalcomposition of Mo_(1.0)V_(0.3)Te_(0.23)Nb_(0.17)Pd_(0.01)O_(x). 30 g ofthe catalyst were ground and added to 100 mL solution of 30% oxalic acidin water. The resulting suspension was stirred at 125° C. for 5 hrs in aParr reactor, then the solids were collected by gravity filtration anddried in a vacuum oven overnight at 25° C.

The dried material from above, sized to ≦75 microns was impregnated byincipient wetness with an aqueous solution of platinic acid to result ina 0.01 molar loading of Pt with respect to Mo. The excess water wasremoved via a rotary evaporator at a temperature of 50° C. and apressure of 28 mm Hg and then calcined in a quartz tube at 600° C. underan Ar flow of 100 cc/min for two hours. The resulting material wasground, sized to ≦75 microns, suspended in acetone (1 g/10 cc) andsonicated for 30 minutes. A 45 ppi alpha alumina foam (Vesuvius Hi-Techof dimensions 12 mm diameter and 0.5 cm thickness) was dipped into thestirring catalyst/acetone suspension and then dried at room temperatureunder N₂ several times until no further weight gain was observed for thewash coated foam. Alternating sides of the foam were oriented for eachcycle of wash coating which prevented clogging of foam's pores. Theresulting wash coated foam weighed 0.112 g and consisted of 20 wt %catalyst.

Comparative Example 2 Pt/In Oxides Supported on α-Alumina Foam Monoliths

Alpha-Al₂O₃ foam monoliths (45 pores per inch) were employed as supportsin the preparation of two sets of catalysts. The first set comprises ofsix catalysts made with platinum and indium oxide of assorted ratios asspecified in Table I. Five aqueous solutions of 8% H₂PtCl₆ (platinicacid) were spiked with various amounts of In (NO₃)₃. 5H₂O to generatemixtures with platinum; niobium ratios specified in Table 1. Thesemixtures were kept with stirring at 40 c until homogeneous solutionswere obtained (˜30 min.). To each of the five mixtures three monolithswere added. The catalyst preparation was carried out by immersing themonoliths in the corresponding solutions at ambient temperature for onehour, followed by a drying step (100 c, 1 hr, N2), and finally, by acalcination step (600 c, 4 hr, air). This process was repeated twice(the “pearl” procedure). One catalyst from the above series(Pt:In=1:1.78) was prepared by a different method-the “sequentialcoating process”. In this procedure, the monoliths were first treatedwith indium nitrate solution for one hour, followed by a drying andcalcination steps mentioned above. This was followed by platinum coatingstep. The weights and the percent metals loadings are summarized inTable 1.

TABLE 1 Aluminum Foam-Platinum/Indium Oxides Catalysts. CatalystCatalyst Ratio Support Weight 1^(ST) % Weight 2^(ND) % # Pt/InWeight(g)** application Loading application Loading 1 10:1    1.8271.872 2.46 1.900 3.99 2 3.3:1   1.901 1.947 2.41 1.981 4.21 3 2:1  1.708 1.787 4.63 1.821 6.62 4 1:1.78 1.748 1.806 3.32 1.822 4.23  4*1:1.78 1.757 1.958 11.43 1.971 12.58 5 1:5.4  1.682 1.749 3.98 1.74911.83? *“Sequential procedure” **Weight of three monoliths

Comparative Example 3 Pt/Nb Oxides Supported on α-Alumina Foam Monoliths

Alpha-Al₂O₃ foam monoliths (45 pores per inch) were employed as supportsin the preparation of two sets of catalysts. The first set comprises ofsix catalysts made with platinum and indium oxide of assorted ratios asspecified in Table 2. Five aqueous solutions of 8% H₂PtCI₆ (platinicacid) were spiked with various amounts of aqueous solution of ammoniumniobium oxalate (0.17M Nb) to generate mixtures with platinum; niobiumratios specified in Table 1. These mixtures were kept with stirring at40 c until homogeneous solutions were obtained (˜30 min.). To each ofthe five mixtures three monoliths were added. The catalyst preparationwas carried out by immersing the monoliths in the correspondingsolutions at ambient temperature for one hour, followed by a drying step(100 c, 1 hr, N2), and finally, by a calcination step (600 c, 4 hr,air). This process was repeated twice (the “pearl” procedure). Theresults are summarized in Table 2.

TABLE 2 Aluminum Foam-Platinum/Niobium oxides catalysts. CatalystCatalyst Ratio Support Weight 1^(ST) % Weight 2^(ND) % # Pt/NbWeight(g)** application Loading application Loading 1 10:1  2.080 2.1071.30 2.126 2.21 2 10:3  1.824 1.842 0.98 1.871 2.58 3 1:1 1.855 1.8841.56 1.907 2.91 4 1:3 1.852 1.891 2.11 1.901 2.65 5  1:10 1.762 1.7911.65 1.820 3.30

Comparative Example 4 Pt/Nb/V Oxides Supported on α-Alumina FoamMonoliths

Alpha-Al₂O₃ foam monoliths (45 pores per inch) were employed as supportsin the preparation of Pd—Nb—V catalyst. A solution made of 8% Pd(palladium nitrate hydrate), 2% In (Indium nitrate hydrated), 0.4% V(ammonium metavanadate), oxalic acid (5 weight %) was kept with stirringat 40° C. Conc Nitric acid was added to generate a homogeneous solutionof 2.0 pH. The catalyst preparation was carried out by immersing themonoliths in the corresponding solution at ambient temperature for onehour, followed by a drying step (100 c, 1 hr, N₂), and, finally, by acalcination step (600 c, 4 hr, air). This process was repeated twiceresulted in 4.7% loading.

Comparative reactor data for propane conversion using the catalystsystems in a short contact time reactor (SCTR) of the invention arepresented in Table 3.

TABLE 3 SCTR propane data for comparative catalyst systems of theinvention Propane/ Propane Propylene Acrylic acid Propionic acidCatalyst* loading Flow Oxygen N2(%) preheat conversion(%) yield (%)yield (%) yield (%) Pt/In 10:1 2 1.4 15% 200 64 21 0 0 Pt/In 3.3:1  21.4 15% 200 73 19 0 0 Pt/In  2:1 2 1.4 15% 200 73 18 0 0 Pt/In   1:5.4 21.4 15% 200 81 15 0 0 Pt/Nb 10:1 2 1.4 15% 200 59 19 0 0 Pt/Nb 3.3:1  21.4 15% 200 49 15 0 0 *All catalysts were washcoated on a 45 ppialpha-alumina foam, 5 mm long and 12 mm in diameter

Table 4 summarizes physical properties of the molten salt method forpreparing mixed metal oxide catalysts and catalyst systems.

TABLE 4 Selected Properties of Metal Halides Niobium Vanadium TelluriumMolybdenum mp mp mp mp Salt (° C.) Salt (° C.) Salt (° C.) Salt (° C.)NbBr5 265 TeBr2 210 NbC15 205 VCl4 −25.7 TeCl4 224 MoCl5 194 NbF5 72

Multi-Staged Catalyst System Example 1

The first catalyst uses propane as fuel with molecular oxygen togenerate a milder oxidant, carbon dioxide and steam, which reduces thetemperature of the conversion to propane to propylene at short contacttime. The amount of propane sacrificed as fuel and to generate carbondioxide is sufficient (5 to 30% by weight) to generate the amount ofheat needed for the second catalytic stage, the catalyticdehydrogenation of propane to propylene. An exemplary first catalystcomprises a metal selected from Group 8, Pt, Rh, Pd, Ir in the form of agauze, mesh, wires and combinations thereof. The catalysts isunsupported or is supported on a three-dimensional structure including afoam, monolith, coated channel or microreactor that is selected fromsilica, alumina, silicates, aluminosilicates and zeolites. The reactionis conducted at contact times on the order of milliseconds and attemperatures greater than 700° C.

The exotherm generated from the full propane oxidation is used toprovide heat for the endothermic dehydrogenation of propane to propyleneunder steam cracking conditions. In addition any hydrogen generated isused as fuel for the conversion of alkane to its corresponding alkene.Another advantage to the invention is from use of hyrdrogen as a fuel inthe conversion, consistent with work on C2 conversions reported by L.Schmidt et al. The steam cracking catalysts comprises an activatedzeolite, ZSM-5, that has been ion exchanged or framework substituted tooptimize it cracking efficiency. In Superflex technology it has beenreported that incorporation of phosphorus into ZSM-5 improves the FCCperformance at residence times on the order of a second. The reaction iscarried out under short contact times and temperatures greater than 500C. The effluent from the short contact time is directed to a third stageor catalytic structure for selective oxidation. It is also useful atthis stage to add one or more additional oxidants selected from air,oxygen, carbon dioxide and nitrous oxide, including additional steam.Useful or desirable oxygenates produced include acrylic acid, acrolein,acrylic acid esters, methacrylic acid and methacrylic acid esters.Esters require additional staging for alcohols and higher analogues alsorequire appropriate additional staging. The selective oxidations arecarried out at temperatures above 300° C. Mixed metal oxide catalystsare useful.

The multi-staged catalysts are situated in a tubular reactor in serieswith the appropriate catalysts staging as described. Additional heat maybe supplied to the second and third stage catalytic zones as needed toachieve useful conversion yields. Integrated catalytic zones are alsousefully employed that are thermally integrated for optimized nergybalances. The structure may comprise an effective heat exchange materialincluding alloys of Fe—Cr—Al-oxides. The catalysts may be supported onalumina monoliths. Other types of staged catalysts are also usefullyemployed.

Multi-Staged Catalyst System Example 2

Isobutane was catalytically converted to methacrylic acid at shortcontact times using a Pt/Na—[Fe]-ZSM-5 type. This catalyst has beendemonstrated to exhibit high selectivity by L. Schmidt et al. in theconversion of propane to propylene in conventional oxidativedehydrogenation. Addition of low levels of Pt will make the catalystsuitable for flame temperatures in a SCTR. Incorporation of phosphorusinto ZSM-5 is expected to further improve selectivity and yield atconstant alkane conversion. The effluent gaseous stream is directed to asecond catalytic zone for selective oxidation. It is also useful at thisstage to add one or more additional oxidants selected from air, oxygen,carbon dioxide and nitrous oxide, including additional steam and fuel inthe form of oxidized hydrogen. In addition any hydrogen generated isused as fuel for the conversion of alkane to its corresponding alkene.Another advantage to the invention is from use of hydrogen as a fuel inthe conversion, consistent with work on C2 conversions reported by L.Schmidt et al. Useful or desirable oxygenates produced includemethacrylic acid and methacrylic acid esters. Esters require additionalstaging for alcohols and higher analogues also require appropriateadditional staging. The selective oxidations are carried out attemperatures above 300° C. Mixed metal oxide catalysts are useful.

1-10. (canceled)
 11. A multi-stage method for preparing C₃-C₈ alkenesfrom corresponding C₃-C₈ alkanes, comprising the steps of: (A) combining5-30% by weight of a C₃-C₈ alkane, and a stoichiometric amount ofmolecular oxygen, fully oxidizing the alkane to produce carbon dioxide,water vapor, and unreacted alkane; (B) combining the carbon dioxide,water vapor, and unreacted alkane to form a combined feed stream; and(C) contacting the combined feed stream with one or more steam crackingcatalysts at a temperature of from 700° C. to 1000° C. and a residencetime of no greater than 100 milliseconds, to produce the correspondingC₃-C₈ alkene.
 12. The multi-stage method according to claim 11, whereinthe one or more steam cracking catalysts comprise a catalyst systemcumulatively effective at converting the C₃-C₈ alkane to itscorresponding C₃-C₈ alkene and comprising: (1) at least one metalselected from the group consisting of: Ag, Au, Ir, Ni, Pd, Pt, Rh, Ru,alloys thereof and combinations thereof; and (2) at least one modifierselected from the group of metal oxides including the metals Bi, In, Mg,P, Sb, Zr, Group 1-3 metals, lanthanide metals and combinations thereof.13. The multi-stage method according to claim 12, wherein the one ormore steam cracking catalysts further comprise (3) at least one oxide ofa metal selected from the group consisting of: Cd, Co, Cr, Cu, Fe, Mn,Ni, Nb, Ta, V, Zn, and combinations thereof.
 14. A multi-stage methodfor cumulatively converting C₃-C₈ alkanes to their corresponding C₃-C₈oxygenates, comprising the steps of: (A) performing the multi-stagemethod for preparing C₃-C₈ alkenes from corresponding C₃-C₈ alkanesaccording to claim 11, wherein the corresponding C₃-C₈ alkene isproduced; and (B) contacting the corresponding C₃-C₈ alkene with atleast one selective oxidation catalyst comprising at least one metaloxide including the metals Mo, Fe, P, V and combinations thereof, toproduce at least one corresponding C₃-C₈ oxygenate selected from thegroup consisting of: carboxylic acids and esters thereof.
 15. Themulti-stage method according to claim 14, wherein the selectiveoxidation catalyst is separated at a distance downstream from thecracking catalyst.